EP2818930B1 - Verfahren zur konzentrierung des flüssigen abfalls aus der druckplattenherstellung, sowie verfahren zur wiederaufbereitung des flüssigen abfalls aus der druckplattenherstellung - Google Patents

Verfahren zur konzentrierung des flüssigen abfalls aus der druckplattenherstellung, sowie verfahren zur wiederaufbereitung des flüssigen abfalls aus der druckplattenherstellung Download PDF

Info

Publication number
EP2818930B1
EP2818930B1 EP13751553.2A EP13751553A EP2818930B1 EP 2818930 B1 EP2818930 B1 EP 2818930B1 EP 13751553 A EP13751553 A EP 13751553A EP 2818930 B1 EP2818930 B1 EP 2818930B1
Authority
EP
European Patent Office
Prior art keywords
waste liquid
group
liquid
developer
planographic printing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13751553.2A
Other languages
English (en)
French (fr)
Other versions
EP2818930A4 (de
EP2818930A1 (de
Inventor
Mitsuhiro Imaizumi
Toshihiro Watanabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of EP2818930A1 publication Critical patent/EP2818930A1/de
Publication of EP2818930A4 publication Critical patent/EP2818930A4/de
Application granted granted Critical
Publication of EP2818930B1 publication Critical patent/EP2818930B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3092—Recovery of material; Waste processing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/322—Aqueous alkaline compositions

Definitions

  • the present invention relates to a concentrating method and a recycling method of plate-making process waste liquid that is generated, when a photosensitive planographic printing plate precursor is subjected to a plate-making process using an automatic developing machine, by performing a development process and a desensitization process simultaneously in a development processing bath.
  • a means for supplying a developer replenishing liquid to the developer liquid of various steps has been conventionally employed.
  • the performance of the developer liquid is outside the permissible limit even if such replenishment is carried out, all of the developer liquid is discarded. Since plate-making process waste liquid is strongly alkaline, the waste liquid cannot be discharged directly as common drainage, and the plate-making business operator needs to carry out waste liquid processing by installing a waste liquid processing facility, or by outsourcing the process to a waste liquid processing business operator.
  • planographic printing plate-making process waste liquid reducing apparatus which can reduce the amount of discharge of plate-making process waste liquid, and can easily reutilize the water produced during the course of processing plate-making process waste liquid (see, for example, Japanese Patent No. 4774124 ).
  • EP 2 757 417 A1 (prior art pursuant to Art. 54(3) EPC) describes a method for recycling waste water produced by plate-making process.
  • Example 1 thereof refers to a negative-type printing plate. It describes the use of developer liquid including 25% of a surfactant and 1% of potassium hydroxide. According to claim 14 the developer liquid has a pH of 10 to 12.5. It is said that the developer liquid does not include a silicate compound.
  • EP 2 762 977 A1 (prior art pursuant to Art. 54(3) EPC) is directed to a method for recycling plate-making processing waste solution.
  • the developer liquid has a pH from 10 to 13 or 10 to 12.5.
  • Such a liquid comprises a surfactant and an alkali metal hydroxide and does not include a silicate compound.
  • EP 2 163 949 A1 describes a developer for lithographic printing plate precursor and a process for producing lithographic printing plate.
  • JP 2004-070031 describes a method of treating a developer waste liquid produced in the processes of exposing a water developable photosensitive resin plate and then removing the unexposed part with at least water and a developer containing water and a surfactant.
  • the water is vaporized under the conditions of ⁇ 2 atm to separate concentrated liquid containing the resin in the unexposed part from a condensed liquid essentially comprising water.
  • JP 2011-090282 relates to a waste liquid concentrating method. This document describes a positive plate planographic printing plate precursor.
  • the technology of using a flocculant has a problem in that processing of waste liquid requires large expenses, and in a case in which the plate-making process waste liquid contains polymer compounds, there is a problem in that maintenance is complicated, as the solids remaining in the evaporating pot become viscous and adhere to the wall surfaces of the evaporating pot, the evaporating pot is susceptible to contamination, and the piping of the waste liquid processing apparatus is prone to be clogged.
  • the invention has been achieved in consideration of the problems described above, and it is an object of the invention to provide a method of concentrating plate-making process waste liquid, in which, at the time of concentrating waste liquid generated during a plate-making process of simultaneously performing a development process and a desensitization process using a developer liquid in a development processing bath of an automatic developing machine, foaming of the waste liquid is suppressed, and the waste liquid is concentrated efficiently, and washing of the concentrating pot or the like can be easily carried out.
  • the amount of waste liquid can be reduced by simultaneously performing a development process and a desensitization process using a developer liquid in a development processing bath of an automatic developing machine, and the invention can further reduce the amount of waste liquid to be discarded to a large extent, by concentrating the plate-making process waste liquid. Furthermore, foaming is suppressed at the time of concentrating the plate-making process waste liquid, and washing of the concentrating apparatus can be carried out easily.
  • a waste liquid concentrating method of the invention comprises:
  • a photosensitive planographic printing plate precursor an image forming layer on a support is exposed to form a latent image, subsequently non-image areas are removed by development, and thus a planographic printing plate is produced.
  • the photosensitive planographic printing plate precursor used in the invention is a negative type photosensitive planographic printing plate precursor having a radical polymerizable image recording layer, and when exposed regions are cured by polymerization and unexposed areas (non-image areas) are removed by development, ink-receiving image area regions are formed.
  • one of the features lies in that removal of non-image areas and a desensitization process of formed image areas are carried out in a single developing bath of an automatic developing machine, and through this step, the amount of waste liquid is further reduced as compared with the conventional methods.
  • a photosensitive planographic printing plate precursor having a radical polymerizable image recording layer on a support after exposure is subjected simultaneously to a development process and a desensitization process using a developer liquid in a single development processing bath of an automatic developing machine that develops the photosensitive planographic printing plate precursor after exposure, wherein the developer liquid contains from 1% by mass to 10% by mass of a surfactant having a phenyl group or a naphthyl group and at least either an ethylene oxide group or a propylene oxide group, has a content of an organic solvent having a boiling point in a range of from 100°C to 300°C of 2% by mass or less, and substantially does not contain an organic solvent having a boiling point lower than 100°C or higher than 300°C.
  • a developer liquid is used to mean to encompass a development initiating liquid (developer liquid in a narrow sense) and a developer replenishing liquid.
  • the developer liquid and the developer replenishing liquid, to which the invention is applied are a developer liquid for developing a photosensitive planographic printing plate precursor having a radical polymerizable image recording layer, the developer liquid being used to perform a development process and a desensitization process simultaneously in a single development processing bath of an automatic developing machine.
  • the developer liquid of the invention is characterized in that the developer liquid contains from 1% by mass to 10% by mass of a surfactant having either a phenyl group or a naphthyl group, and at least either an ethylene oxide group or a propylene oxide group [hereinafter, appropriately referred to as particular surfactant], has a content of an organic solvent having a boiling point in a range of from 100°C to 300°C of 2% by mass or less, and substantially does not contain an organic solvent having a boiling point lower than 100°C or higher than 300°C.
  • a surfactant having either a phenyl group or a naphthyl group
  • an ethylene oxide group or a propylene oxide group hereinafter, appropriately referred to as particular surfactant
  • the developer liquid does not contain such an organic solvent.
  • the phrase "substantially does not contain an organic solvent having a boiling point lower than 100°C or higher than 300°C” means that the content of an organic solvent having a boiling point lower than 100°C or higher than 300°C is less than 0.2% by mass. It is preferable that the developer liquid according to the invention does not contain an organic solvent having a boiling point lower than 100°C or higher than 300°C.
  • the developer liquid used in the development of a photosensitive planographic printing plate precursor of the invention contains a particular surfactant that will be described below in detail. Also, from the viewpoint that a development process and a desensitization process can be favorably carried out in a single bath, the pH of the developer liquid is from 6.0 to 10.0, and a preferred pH is in the range of from 8.0 to 10.0.
  • the surfactant used in the developer liquid in connection with the waste liquid concentrating method of the invention is not particularly limited as long as the surfactant is a surfactant having either a phenyl group or a naphthyl group and at least either an ethylene oxide group or a propylene oxide group in the molecule.
  • the ethylene oxide group according to the present specification refers to a structure represented by the following Formula (a), and a propylene oxide group refers to a structure represented by the following Formula (b). Having a plurality of these groups means that a plurality of these groups are connected in a straight chain and forms a polyethylene oxide skeleton or a polypropylene oxide skeleton.
  • the surfactant included in the developer liquid is preferably an anionic surfactant or a nonionic surfactant.
  • an anionic surfactant or a nonionic surfactant is used, a wide surfactant concentration latitude can be maintained, and a balance between the liquid penetrability of unexposed areas and the dispersibility of various compounds in the liquid can be achieved.
  • an anionic surfactant that is optimally used in the developer liquid examples include compounds represented by the following Formula (I-A) and Formula (I-B).
  • a preferred developer liquid is a developer liquid for photosensitive planographic printing plate precursor, containing at least one anionic surfactant selected from the group consisting of an anionic surfactant represented by the following Formula (I-A) and an anionic surfactant represented by the following Formula (I-B), at a content in the range of from 1.0% by mass to 10% by mass.
  • each of R 3 and R 5 independently represents a linear or branched alkylene group having from 1 to 5 carbon atoms, the group containing at least one ethylene group or propylene group; each of R 4 and R 6 independently represents a linear or branched alkyl group having from 1 to 20 carbon atoms; each of p and q independently represents 0, 1 or 2; each of Y 1 and Y 2 independently represents a single bond, or an alkylene group having from 1 to 10 carbon atoms; each of n and m independently represents an integer from 1 to 100, and when each of n and m represents any number from 2 to 100, plural R 3 s and plural R 5 s may be identical with or different from each other; and M + represents Na + , K + , Li + or NH 4 + .
  • respective preferred examples of R 3 and R 5 include -CH 2 -, -CH 2 CH 2 -, and -CH 2 CH(CH 3 )-, and at least one represents -CH 2 CH 2 - or -CH 2 CH(CH 3 )-.
  • Each of R 3 and R 5 is more preferably -CH 2 CH 2 -.
  • preferred examples of R 4 and R 6 include CH 3 , C 2 H 5 , C 3 H 7 , and C 4 H 9 .
  • Each of p and q is preferably 0 or 1.
  • Each of Y 1 and Y 2 is preferably a single bond.
  • Each of n and m is preferably an integer from 3 to 50, and more preferably an integer from 5 to 30.
  • Formula (II-A) and Formula (II-B) each of R 1 and R 2 independently represents a hydrogen atom or an alkyl group having from 1 to 100 carbon atoms; and each of n and m independently represents an integer from 0 to 100, provided that n and m are not simultaneously 0.
  • Specific examples of the compound represented by Formula (II-A) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether.
  • Specific examples of the compound represented by Formula (II-B) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, and polyoxyethylene nonyl naphthyl ether.
  • the number of repeating units (n) of the polyoxyethylene group is preferably from 3 to 50, and more preferably from 5 to 30.
  • the number of repeating units (m) of the polyoxypropylene group is preferably from 0 to 10, and more preferably from 0 to 5.
  • the bonding between an oxyethylene group and an oxypropylene group may be random bonding or block bonding.
  • nonionic aromatic ether-based surfactants represented by Formula (II-A) and Formula (II-B) When nonionic aromatic ether-based surfactants represented by Formula (II-A) and Formula (II-B) are used, the surfactants may be used singly, or two or more kinds thereof may be used in combination in the developer liquid.
  • the particular surfactants described above can be used singly or in combination of plural kinds thereof. When two or more kinds are used in combination, any of an aspect including two or more kinds of the particular anionic surfactants only, an aspect including two or more kinds of the particular nonionic surfactants, and an aspect including one or more kinds of each of the particular anionic surfactant and the particular nonionic surfactant, may be used.
  • the amount of addition of the particular surfactant needs to be in the range of from 1% by mass to 10% by mass in the developer liquid, and the amount of addition is preferably in the range of from 2% by mass to 10% by mass, and more preferably in the range of from 3% by mass to 10% by mass, from the viewpoint of the effect.
  • the amount of addition of the particular surfactant in the developer liquid is adjusted to 1% by mass or more, favorable developability and favorable solubility of the image recording layer components in the developer liquid are obtained, and when the amount of addition is adjusted to 10% by mass or less, printing durability of the planographic printing plate thus formed becomes favorable.
  • the amount of addition represents the total amount.
  • the developer liquid used in the invention may include, in addition to the particular surfactant described above, another surfactant (a surfactant having a structure different from that of the particular surfactant, for example, a surfactant which does not contain any of a phenyl group or a naphthyl group, and an ethylene oxide group or a propylene oxide group) to the extent that the effects of the invention are not impaired.
  • another surfactant a surfactant having a structure different from that of the particular surfactant, for example, a surfactant which does not contain any of a phenyl group or a naphthyl group, and an ethylene oxide group or a propylene oxide group
  • Examples of the other surfactant that can be additionally used include betaine-type surfactants represented by the following Formula ⁇ 1>, Formula ⁇ 2>, or Formula ⁇ 3>:
  • R 1 represents a hydrogen atom, an alkyl group, or a substituent having the structure described below;
  • A represents a hydrogen atom, an alkyl group, a monovalent substituent containing an ethylene oxide group, a monovalent substituent containing a carboxylic acid group, or a monovalent substituent containing a carboxylic acid salt;
  • B represents a monovalent substituent containing an ethylene oxide group, a monovalent substituent containing a carboxylic acid group, or a monovalent substituent containing a carboxylic acid salt.
  • R 8 represents a hydrogen atom or an alkyl group.
  • each of R 2 and R 3 independently represents a hydrogen atom, or an alkyl group which may have a substituent, and at least one of R 2 or R 3 represents an alkyl group which may have a substituent.
  • D represents an alkyl group or a monovalent substituent containing an ethylene oxide group
  • E represents a monovalent substituent containing a carboxylate anion, or a monovalent substituent containing an oxide anion (O - ).
  • each of R 4 , R 5 , R 6 , and R 7 independently represents a hydrogen atom or an alkyl group, and Z - represents a counter anion.
  • the ethylene oxide group contained in the monovalent substituent containing an ethylene oxide group means -(CH 2 CH 2 O) n H (wherein n represents an integer of 1 or larger, and preferably from 2 to 20), and the monovalent substituent containing an ethylene oxide group as used herein is intended to also encompass an ethylene oxide group.
  • the monovalent substituent containing a carboxylic acid group also encompasses the case of a carboxylic acid group only.
  • a carboxylic acid salt of a group containing a carboxylic acid salt means -COOM, and M represents an alkali metal or an alkaline earth metal, and is preferably an alkali metal.
  • the monovalent substituent containing a carboxylic acid salt also encompasses the case of a carboxylic acid salt only.
  • the monovalent substituent containing a carboxylate anion also encompasses the case of a carboxylate anion only.
  • the monovalent substituent containing an oxide anion (O - ) also encompasses the case of an oxide anion only.
  • the compound represented by Formula ⁇ 1>, Formula ⁇ 2>, or Formula ⁇ 3> (hereinafter, also referred to as particular betaine type surfactant) is not particularly limited, but representative examples include compounds represented by the following Formula (I) to Formula (V):
  • examples of the particular betaine type surfactant also include a surfactant represented by the following Formula (VI):
  • R 11 represents a hydrogen atom; an alkyl group; or an alkyl group linked through a bond selected from an ester bond, a carbonyl bond and an amide bond.
  • the number of carbon atoms of the alkyl group linked through the bond described above is preferably from 8 to 20.
  • Each of R 12 , R 15 , R 18 and R 24 to R 29 independently represents a hydrogen atom or an alkyl group.
  • R 13 represents an alkyl group or a monovalent substituent containing an ethylene oxide group.
  • R 16 represents a hydrogen atom, an alkyl group, or a monovalent substituent containing an ethylene oxide group.
  • R 21 represents a hydrogen atom, an alkyl group, or a group shown below: wherein R* represents a hydrogen atom or an alkyl group.
  • R 30 represents an alkyl group, or a group containing an ethylene oxide group.
  • Each of R 14 , R 17 , R 19 , R 20 , R 22 , R 23 and R 31 independently represents an alkylene group or a single bond.
  • N and the carboxyl group may be directly linked, and in this case, R 14 represents a single bond.
  • R 14 represents a single bond.
  • the surfactant represented by Formula (I) when the total number of carbon atoms increases, the hydrophobic moiety becomes larger, and dissolution in a water-based developer liquid is made difficult. In this case, dissolution is ameliorated by mixing an organic solvent which helps dissolution, or a dissolution aid such as an alcohol, into water; however, if the total number of carbon atoms becomes too large, the surfactant cannot be dissolved within an adequate extent of mixing.
  • the sum of the numbers of carbon atoms of R 11 to R 14 is preferably from 10 to 40, and more preferably from 12 to 30.
  • R 11 to R 13 described above represent alkyl groups, or R 14 represents an alkylene group
  • the structure may be linear, or may be branched.
  • the number of carbon atoms of R 11 to R 14 in these compounds is affected by the material used in the image recording layer, particularly a binder.
  • a binder having a higher degree of hydrophilicity there is a tendency that relatively smaller numbers of carbon atoms of R 11 to R 14 are preferable, and when the binder used has a lower degree of hydrophilicity, it is preferable that the numbers of carbon atoms of R 11 to R 14 are larger.
  • betaine type surfactant represented by Formula (I) include compounds shown below.
  • R 15 in the formula represents a hydrogen atom or an alkyl group
  • R 16 represents a hydrogen atom, an alkyl group, or a monovalent substituent containing an ethylene oxide group
  • R 17 represents an alkylene group or a single bond.
  • the sum of the number of carbon atoms of R 15 to R 17 is preferably from 10 to 30, and more preferably from 12 to 25.
  • R 15 and R 16 are alkyl groups, or R 17 is an alkylene group, the structures thereof may be straight-chained, or may be branched.
  • the number of carbon atoms of R 15 to R 17 in the betaine type surfactant represented by Formula (II) is appropriately selected in relation to the other materials used in the image recording layer. For example, when a binder having a higher degree of hydrophilicity is used in combination, relatively smaller numbers of carbon atoms of R 15 to R 17 are preferred, and when a binder having a lower degree of hydrophilicity is used in combination, larger numbers of carbon atoms of R 15 to R 17 are preferred.
  • a monovalent metal ion such as a potassium ion or a sodium ion
  • a divalent metal ion such as a calcium ion or a magnesium ion
  • an ammonium ion such as a hydrogen ion; or the like
  • a sodium ion or a potassium ion is particularly preferred.
  • Representative examples of the surfactant represented by Formula (II) include compounds shown below.
  • R 18 represents a hydrogen atom or an alkyl group; and each of R 19 and R 20 represents an alkylene group or a single bond.
  • the sum of the numbers of carbon atoms of R 18 to R 20 is preferably from 10 to 30, and more preferably from 12 to 28.
  • R 18 is an alkyl group
  • R 19 and R 20 are alkylene groups
  • the structures thereof may be straight-chained, or may be branched.
  • the number of carbon atoms of R 18 to R 20 in the betaine type surfactant represented by Formula (III) is appropriately selected in relation to the other materials used in the image recording layer. For example, when a binder having a higher degree of hydrophilicity is used in combination, relatively smaller numbers of carbon atoms of R 18 to R 20 are preferred, and when a binder having a lower degree of hydrophilicity is used in combination, larger numbers of carbon atoms of R 18 to R 20 are preferred.
  • a monovalent metal ion such as a potassium ion or a sodium ion
  • a divalent metal ion such as a calcium ion or a magnesium ion
  • an ammonium ion a hydrogen ion; or the like
  • a sodium ion or a potassium ion is particularly preferred.
  • Representative examples of the compound include compounds shown below.
  • N and ethylene oxide may be directly linked, and in this case, R 22 and R 23 represent single bonds.
  • the sum of the numbers of carbon atoms of R 21 to R 23 is preferably from 8 to 50, and more preferably from 12 to 40.
  • R 21 represents an alkyl group
  • R 22 and R 23 represent alkylene groups
  • the structures thereof may be straight-chained, or may be branched.
  • the numbers of carbon atoms of R 21 to R 23 in the surfactant represented by Formula (IV) are appropriately selected in relation to the other materials used in the image recording layer. For example, when a binder having a higher degree of hydrophilicity is used in combination, relatively smaller numbers of carbon atoms of R 21 to R 23 are preferred, and when a binder having a lower degree of hydrophilicity is used in combination, larger numbers of carbon atoms of R 21 to R 23 are preferred.
  • m and n that represent the numbers of ethylene oxide moieties, when these values are larger, the degree of hydrophilicity is increased, and stability in water is increased, m and n may represent the same number, or may represent different numbers.
  • the sum of m and n is preferably from 3 to 40, and more preferably from 5 to 20.
  • Representative examples of the compound include compounds shown below.
  • each of R 24 to R 27 in the formula represents a hydrogen atom or an alkyl group.
  • the sum of the numbers of carbon atoms of R 24 to R 27 is preferably from 10 to 30, and more preferably from 12 to 28.
  • R 24 to R 27 described above are alkyl groups, the structures thereof may be straight-chained, or may be branched.
  • the numbers of carbon atoms of R 24 to R 27 in the surfactant represented by Formula (V) are appropriately selected in relation to the other materials used in the image recording layer. For example, when a binder having a higher degree of hydrophilicity is used in combination, relatively smaller numbers of carbon atoms of R 24 to R 27 are preferred, and when a binder having a lower degree of hydrophilicity is used in combination, larger numbers of carbon atoms of R 24 to R 27 are preferred.
  • Z - represents a counter anion.
  • Cl - , Br - , I - , and the like are used.
  • Representative examples of the compound include compounds shown below.
  • each of R 21 and R 29 in the formula represents a hydrogen atom or an alkyl group; and R 30 represents an alkyl group, or a monovalent substituent containing an ethylene oxide group.
  • the sum of the numbers of carbon atoms of R 28 to R 30 is preferably from 8 to 30, and more preferably from 10 to 28.
  • R 28 to R 30 are alkyl groups, the structures thereof may be straight-chained, or may be branched.
  • the numbers of carbon atoms of R 28 to R 30 in the surfactant represented by Formula (VI) are appropriately selected in relation to the other materials used in the image recording layer. For example, when a binder having a higher degree of hydrophilicity is used in combination, relatively smaller numbers of carbon atoms of R 28 to R 30 are preferred, and when a binder having a lower degree of hydrophilicity is used in combination, larger numbers of carbon atoms of R 21 to R 30 are preferred.
  • Representative examples of the compound include compounds shown below.
  • the particular betaine type surfactant which is the other surfactant, is usually incorporated as desired into the developer liquid used in the invention, but may also be incorporated in order to improve dispersibility of the components of a developed image recording layer, provided that the content thereof is preferably less than 10% by mass with respect to the developer liquid. If the content of the particular betaine type surfactant is 10% by mass or more, there is a possibility that the members in the developing bath are subjected to erosion, which becomes a cause of apparatus failure, and thus such a content is not preferable.
  • the developer liquid/developer replenishing liquid used for the development of a photosensitive planographic printing plate precursor may contain an organic solvent having a boiling point in the range of from 100°C to 300°C for the purpose of enhancing the solubility of the image recording layer components, or the like.
  • the content should be adjusted to the range of 2% by mass or less, and it is also preferable that the organic solvent is not included.
  • the boiling point of the organic solvent included in the developer liquid is lower than 100°C, the organic solvent is likely to be volatilized, and if the boiling point is higher than 300°C, it is more difficult to concentrate the developer liquid, and it is not preferable.
  • any organic solvent may be used as long as the boiling point is in the range of from 100°C to 300°C, and preferred examples include 2-phenylethanol (boiling point: 219°C), 3-phenyl-1-propanol (boiling point: 238°C), 2-phenoxyethanol (boiling point: 244°C to 255°C), benzyl alcohol (boiling point: 205°C), cyclohexanol (boiling point: 161°C), monoethanolamine (boiling point: 170°C), diethanolamine (boiling point: 268°C), cyclohexanone (boiling point: 155°C), ethyl lactate (boiling point: 155°C), propylene glycol (boiling point: 187°C), ethylene glycol (boiling point: 198°C), ⁇ -butyrolactone (boiling
  • amines of the alkali agent that will be described below are also handled as organic solvents in the invention, as long as the boiling points thereof are in the range of from 100°C to 300°C.
  • the developer liquid according to the invention includes the particular anionic surfactant and/or particular nonionic surfactant described above, and an alkali agent that will be described below, and has a pH value of from 6 to 10.
  • the pH of the developer liquid may be adjusted using a pH adjusting agent.
  • the developer liquid contains an organic carboxylic acid such as citric acid, malic acid, tartaric acid, gluconic acid, benzoic acid, phthalic acid, p-ethylbenzoic acid, p-n-propylbenzoic acid, p-isopropylbenzoic acid, p-n-butylbenzoic acid, p-t-butylbenzoic acid, p-t-butylbenzoic acid, p-2-hydroxyethylbenzoic acid, decanoic acid, salicylic acid or 3-hydroxy-2-naphthoic acid, or a metal salt, ammonium salt, or the like thereof.
  • organic carboxylic acid such as citric acid, malic acid, tartaric acid, gluconic acid, benzoic acid, phthalic acid, p-ethylbenzoic acid, p-n-propylbenzoic acid,
  • citric acid has a function as a buffering agent, and citric acid is added as, for example, trisodium citrate or tripotassium citrate.
  • one kind or two or more kinds of the buffering agents are incorporated into the developer liquid in an amount in the range of from 0.05% to 5% by mass, and more preferably from 0.3% to 3% by mass.
  • a water-soluble polymer compound may be incorporated in order to reinforce the function of protecting plate surfaces as a gum fluid during the desensitization process that is carried out together with development in a developing bath.
  • water-soluble polymer compound used in the developer liquid according to the invention examples include soybean polysaccharides, modified starches, gum arabic, dextrin, cellulose derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose, and methyl cellulose) and modification products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylamide and acrylamide copolymers, a vinyl methyl ether/maleic anhydride copolymer, a vinyl acetate/maleic anhydride copolymer, and a styrene/maleic anhydride copolymer.
  • a preferred acid value of the water-soluble polymer compound is from 0 meq/g to 3.0 meq/g.
  • soybean polysaccharides those conventionally known materials can be used, and for example, there is available SOYAFIBE (manufactured by Fuji Oil Co., Ltd.) as a commercially available product, and products of various grades can be used.
  • SOYAFIBE manufactured by Fuji Oil Co., Ltd.
  • a product that can be preferably used is such that the viscosity of a 10 mass% aqueous solution is in the range of from 1 mPa/sec to 100 mPa/sec.
  • a compound represented by the following Formula (VII) is preferred.
  • any starch obtained from corn, potato, tapioca, rice, wheat and the like can be used. Modification of these starches can be carried out by a method of decomposing starch using an acid, an enzyme or the like such that the number of glucose residues per molecule would be in the range of from 5 to 30, and further adding oxypropylene in an alkali, or the like.
  • the degree of etherification (degree of substitution) is in the range of from 0.05 to 1.2 per glucose unit; n represents an integer from 3 to 30; and m represents an integer from 1 to 3.
  • water-soluble polymer compounds include soybean polysaccharides, modified starches, gum arabic, dextrin, carboxymethyl cellulose, and polyvinyl alcohol.
  • the water-soluble polymer compounds can be used in combination of two or more kinds.
  • the content of the water-soluble polymer compound in the developer liquid is preferably from 0.1% to 20% by mass, and more preferably from 0.5% to 10% by mass.
  • a chelating agent for a divalent metal may also be incorporated into the developer liquid.
  • a divalent metal include magnesium and calcium.
  • the chelating agent include, for example, Na 2 P 2 O 7 , Na 5 P 3 O 3 , Na 3 P 3 O 9 , Na 2 O 4 P(NaO 3 P)PO 3 Na 2 ; polyphosphates such as CALGON (sodium polymetaphosphate); aminopolycarboxylic acids such as, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraaminehexaacetic acid, potassium salt thereof, sodium salt thereof; hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof; nitrilotriacetic acid, potassium salt thereof, sodium salt thereof; 1,2-diaminocyclohexanetetraacetic acid, potassium salt thereof, sodium salt thereof; 1,3-
  • the content of such a chelating agent in the developer liquid may vary with the hardness and the amount of use of the hard water used in the developer liquid; however, in general, the chelating agent is incorporated in an amount in the range of from 0.01% to 5% by mass, and more preferably from 0.01% to 0.5% by mass, in the developer liquid.
  • a defoamant may be added to the developer liquid.
  • a fluorine-containing defoamant a silicone-based defoamant, acetylene alcohol, or acetylene glycol may also be incorporated as the defoamant.
  • fluorine-containing defoamant examples include compounds represented by the formula described below.
  • a fluorine-containing defoamant having an HLB value of from 1 to 9, particularly a fluorine-containing defoamant having an HLB value of from 1 to 4, is preferably used.
  • the fluorine-containing defoamants described above are added to the developer liquid directly, or in the form of an emulsion mixed with water or a solvent other than that.
  • R represents a hydrogen atom or an alkyl group
  • Rf represents a fluorocarbon group (having from about 5 to 10 carbon atoms) in which some or all of the hydrogen atoms of the alkyl group have been substituted by fluorine atoms
  • X represents CO or SO 2
  • n represents an integer from 1 to 10.
  • a dialkylpolydioxane preferably a dimethylpolydioxane described below
  • a dialkylpolydioxane is used directly or as a O/W type emulsion: an alkoxypoly(ethyleneoxy)siloxane described below, a dimethylpolydioxane modified by partially introducing carboxylic acid groups or sulfonic acid groups thereto, or an emulsion obtained by mixing such a silicone compound with water together with a compound generally known as an anionic surfactant, is used.
  • R' alkyl group having from 1 to 4 carbon atoms
  • m 2 to 4, n: 4 to 12, R": alkyl group having from 1 to 4 carbon atoms
  • An acetylene alcohol is an unsaturated alcohol having an acetylene bond (triple bond) in the molecule.
  • an acetylene glycol is also called an alkynediol, and is an unsaturated glycol having an acetylene bond (triple bond) in the molecule.
  • R 1 represents a linear or branched alkyl group having from 1 to 5 carbon atoms.
  • R 2 and R 3 independently represents a linear or branched alkyl group having from 1 to 5 carbon atoms; and a+b represents a number from 0 to 30.
  • examples of the linear or branched alkyl group having from 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an isopentyl group.
  • acetylene alcohols and acetylene glycols are available from the market, and examples of commercially available products include trade name: SURFINOL manufactured by Air Products and Chemicals, Inc.
  • Specific examples of the commercially available products include, as the item (3) described above, SURFINOL 61; as the item (4), ORFIN B; as the item (5), ORFIN P; as the item (7), ORFIN Y; as the item (8), SURFINOL 82; as the item (9), SURFINOL 104, and ORFIN AK-02; as the item (10), SURFINOL 400 series; and as the item (11), SURFINOL DF-110D.
  • an alkali metal salt of an organic acid, or an alkali metal salt of an inorganic acid may also be added, as a development regulating agent, to the developer liquid.
  • sodium carbonate, potassium carbonate, ammonium carbonate, sodium citrate, potassium citrate, ammonium citrate, and the like may be used singly or in combination of two or more kinds thereof.
  • inorganic alkali agents such as tribasic sodium phosphate, tribasic potassium phosphate, tribasic ammonium phosphate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, and lithium hydroxide
  • organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, pyridine, and tetramethylammonium hydroxide, may be used singly or in combination of two or more kinds thereof.
  • the developer liquid may contain the following additional components if necessary, in addition to the components described above. Examples thereof include a reducing agent, a dye, a pigment, a hard water softening agent, and a preservative.
  • the pH of the developer liquid used herein is preferably from 6.0 to 11.0, and more preferably from 8.0 to 10.0, from the viewpoint of the effect.
  • the remaining component of the developer liquid described above is water. It is advantageous, in view of transportation, to have the developer liquid (developer stock solution) according to the invention prepared as a concentrated liquid with a reduced content of water, so that the concentrated liquid may be diluted with water at the time of use.
  • the degree of concentration in this case is appropriately such that the various components would not undergo separation or precipitation.
  • a development process and a desensitization process can be carried out favorably in a single bath by using the developer liquid described above in the developing bath of a general automatic developing machine.
  • the development process can be carried out by a conventional method at a temperature of from 0°C to 60°C, and preferably from 15°C to 40°C, for example, by a method of immersing an imagewise exposed photosensitive planographic printing plate precursor in a developer liquid, and scrubbing the printing plate precursor with a brush; a method of spraying a developer liquid by spraying, and scrubbing the printing plate precursor with a brush; or the like.
  • the development processing step according to the invention can be suitably carried out using an automatic development processing machine equipped with a developer liquid supplying means and a scrubbing member.
  • An automatic development processing machine using a rotating brush roll as a scrubbing member is particularly preferred.
  • the automatic development processing machine includes a means for removing any excess developer liquid, such as a squeeze roller, or a drying means such as a hot air blowing apparatus, after the development processing means.
  • the automatic development processing machine may also include a heating means for heat treating the imagewise exposed photosensitive planographic printing plate precursor, before the development processing means.
  • Processing with such an automatic development processing machine is advantageous in that there is no need to handle the development residue originating from the protective layer/image recording layer, which is generated in the case of a so-called on-press development process.
  • plate-making process waste liquid produced by the plate-making processing step is evaporatively concentrated with a waste liquid concentrating apparatus such that the ratio of the volume of the plate-making process waste liquid after concentration to the volume of the plate-making process waste liquid before concentration would be from 1/2 to 1/10.
  • the waste liquid concentrating apparatus includes at least an evaporating pot (not shown in the diagram) that heats waste liquid without performing pressure reduction or under reduced pressure, and separates the waste liquid into water that evaporates and a concentrate (slurry) that remains; and a cooling pot (not shown in the diagram) that cools and condenses the water separated as water vapor, which may contain an organic solvent, in the evaporating pot, and produces reclaimed water.
  • concentration of the waste liquid is carried out by a method of reducing the pressure inside the evaporating pot using a pressure reducing means, and heating and concentrating the waste liquid, because the boiling point of the waste liquid is decreased, and the waste liquid can be evaporatively concentrated at a lower temperature than at atmospheric pressure.
  • a pressure reducing means is used, there is an advantage that it is safer, and the evaporating pot, the waste liquid and the waste liquid concentrate are not easily affected by heat.
  • Examples of the pressure reducing means include general mechanical vacuum pumps of water seal type, oil rotation type, diaphragm type and the like, diffusion pumps using oil or mercury; compressors such as a multi-stage turbo compressor, a reciprocating compressor, or a screw compressor; and aspirators. Among these, an aspirator is preferably used from the viewpoints of maintenance performance and cost.
  • pressure can be reduced to a value of from 666.6 Pa (5 mmHg) to 13332.2 Pa (100 mmHg), and preferably from 666.6 Pa (5 mmHg) to 3999.7 Pa (30 mmHg).
  • a temperature range corresponding to 666.6 Pa to 13332.2 Pa which is a pressure range that can be easily obtained by a tap aspirator or a vacuum pump, is selected.
  • the temperature is in the range of from 20°C to 80°C, and more preferably in the range of from 25°C to 45°C.
  • a heat pump as the heating means in the evaporating pot, and regarding the heat pump, an aspect including a heat releasing unit and a heat absorbing unit is preferred.
  • the plate-making process waste liquid is heated by the heat releasing unit of the heat pump, and the water vapor separated from the plate-making process waste liquid can be cooled by the heat absorbing unit of the heat pump.
  • the thermal efficiency is favorable, and as compared with the case of using a heating means such as an electric heater, there are advantages such as that high temperature sites do not occur locally, it is much safer, and the emission amount of carbon dioxide is decreased.
  • the plate-making process waste liquid is evaporatively concentrated in the waste liquid concentrating apparatus
  • the concentration ratio is less than 1/2, reduction of the amount of waste liquid to be processed is not effectively achieved, and when the concentration is achieved at a ratio of more than 1/10, precipitation of solids attributable to the concentrated waste liquid is likely to occur in the evaporating pot of the waste liquid concentrating apparatus 30, and there is a concern that maintenance performance may be deteriorated.
  • concentration is achieved in the range of 1/3 to 1/8 on a volume basis. In the above-described range of concentration, less contamination occurs in the concentrating pot, and continuous operation is enabled over a long time period. Also, the reclaimed water thus obtained can be reutilized, and the amount of waste liquid to be discarded as the plate-making process waste liquid is very small.
  • waste liquid concentrating apparatus used in the present embodiment, commercially available products such as heat pump type concentrating apparatuses, XR-2000 and XR-5000 (all trade names), manufactured by Takagi Refrigerating Co., Ltd., and heating type concentrating apparatuses, FRIENDLY series (trade name), manufactured by Cosmotech Co., Ltd., may be used .
  • the water vapor separated in the waste liquid concentrating step is condensed, and thus reclaimed water is produced.
  • the waste liquid concentrating step when heating and concentration of waste liquid is carried out using a heat pump, the water vapor cooled by the heat absorbing unit of the heat pump turns into a liquid state, and reclaimed water can be obtained. That is, reclaimed water is produced in the waste liquid concentrating step.
  • a known heating means such as an electric heater
  • water vapor is condensed using a cooling means, and thus reclaimed water is produced.
  • a known water cooling cooler or the like may be used as appropriate.
  • the reclaimed water obtainable as described above is reclaimed water with low BOD and COD values.
  • the BOD value is 250 mg/L or less
  • the COD value is 200 mg/L or less. Therefore, excess reclaimed water may be discharged directly into common drainage.
  • the reclaimed water contains an organic solvent or the like, the reclaimed water is subjected to a treatment using activated sludge or the like, before being discharged.
  • a recycling method of the invention comprises:
  • the recycling method of the invention further includes a reclaimed water supplying step in addition to the plate-making processing step, the waste liquid concentrating step, and the reclaimed water producing step of the method of concentrating plate-making process waste liquid of the invention.
  • the reclaimed water thus produced is supplied to a replenishing water tank or the like, and may be used as diluent water for diluting a developer replenishing liquid at a predetermined ratio inside a developing bath disposed in the automatic developing machine, or may be mixed in advance with a developer replenishing liquid to dilute the developer replenishing liquid at a predetermined ratio.
  • reclaimed water produced from the plate-making process waste liquid generated from plural automatic developing machines may be collected in a replenishing water tank at one site and used, and may also be supplied from the replenishing water tank to plural automatic developing machines as diluent water or rinsing water.
  • an automatic developing machine 10 that stores waste liquid of developer liquid discharged from the automatic developing machine 10 as a result of a plate-making process of a photosensitive planographic printing plate precursor; and a waste liquid concentrating apparatus 30 that heats, without performing pressure reduction or under reduced pressure, the waste liquid sent from the intermediate tank 20, separates the waste liquid into evaporating water vapor and a remaining concentrate (slurry), and also cools and condenses the separated water vapor, thereby producing reclaimed water.
  • Reclaimed water is introduced into a reclaimed water tank 50.
  • the waste liquid concentrated in the waste liquid concentrating apparatus 30 is collected into a waste liquid collecting tank 40. Transport of the concentrated waste liquid to the waste liquid tank 40 is preferably carried out by applying pressure using a pump.
  • the waste liquid concentrating apparatus 30 includes at least an evaporating pot (not shown in the diagram) that heats, without performing pressure reduction or under reduced pressure, the waste liquid sent from the intermediate tank 20, and separates the waste liquid into evaporating water vapor and a remaining concentrate (slurry); and a cooling pot (not shown in the diagram) that cools and condenses the water separated as water vapor (may include an organic solvent) in the evaporating pot, and thereby produces reclaimed water.
  • the system includes a reclaimed water tank 50 that temporarily stores the reclaimed water thus separated, and a distilled reclaimed water reutilization apparatus 60 that controls the supply of the reclaimed water to the automatic developing machine 10.
  • the distilled reclaimed water reutilization apparatus 60 preferably includes a replenishing water tank 80 that supplies the reclaimed water to the automatic developing machine 10; a piping; a pressure gauge that measures the pressure inside the piping; and a pump.
  • the apparatus may also include a means that has an analyzer, analyzes the components of the reclaimed water, and performs neutralization, supply of fresh water, and the like according to the components, thereby regulating the composition.
  • the reclaimed water thus collected is supplied from the replenishing water tank 80 to the automatic developing apparatus 10 by controlling the driving of the pump according to the pressure value measured with the pressure gauge equipped in the distilled reclaimed water reutilization apparatus 60.
  • the automatic developing machine 10 is supplied with a developer replenishing liquid from a developer replenishing liquid tank 70.
  • the reclaimed water obtained by this system may contain an organic solvent in an amount of 0.5% or less by volume.
  • the reclaimed water thus obtained is reclaimed water with low BOD and COD values.
  • the BOD value is 250 mg/L or less
  • the COD value is 200 mg/L or less. Therefore, excess reclaimed water may be discharged directly into common drainage, in addition to being used as diluent water for evaporation correction in the automatic developing machine, diluent water for developer replenishing liquid, rinsing water for washing the plate, or washing water of the automatic developing machine.
  • the developer replenishing liquid is diluted and supplied to a developing bath of the automatic developing machine 10.
  • Fig. 1 illustrates an aspect in which the amount of the reclaimed water supplied from the replenishing water tank 80 is controlled according to the amount of supply from the developer replenishing liquid tank 70, and the developer replenishing liquid is diluted at a predetermined ratio in a developing bath (not shown in the diagram) disposed in the automatic developing machine 10; however, the invention is not intended to be limited to this aspect, and the developer replenishing liquid and the reclaimed water may be mixed in advance to dilute the developer replenishing liquid at a predetermined ratio, and then the mixture may be supplied to the developing bath.
  • the plate-making process waste liquid generated from plural automatic developing machines are collected in one waste liquid concentrating apparatus, and the reclaimed water thus obtained is supplied to plural automatic developing machines as diluent water or rinsing water.
  • the invention is also advantageous in that when the reclaimed water is utilized as replenishing water, the throughput of the photosensitive planographic printing plate precursor that is appropriately plate-making processed is increased, without further supplying fresh diluent water or the like.
  • any printing plate precursor having a radical polymerizable image recording layer on a hydrophilic support can be used without any particular limitations.
  • the radical polymerizable image recording layer usually contains (A) a polymerization initiator, (B) a polymerizable compound, and (C) a sensitizing colorant, and if desired, further contains (D) a binder polymer. It is preferable that the photosensitive planographic printing plate precursor includes, on the support, a radical polymerizable image recording layer and a protective layer in this sequence.
  • the image recording layer contains a polymerization initiator (hereinafter, also referred to as initiator compound).
  • a radical polymerization initiator is preferably used.
  • any compound known to those ordinarily skilled in the art can be used without any limitations, and specific examples include a trihalomethyl compound, a carbonyl compound, an organic peroxide, an azo compound, an azide compound, a metallocene compound, a hexaarylbiimidazole compound, an organoboron compound, a disulfone compound, an oxime ester compound, an onium salt compound, and an iron-arene complex.
  • the initiator compound is preferably at least one selected from the group consisting of a hexaarylbiimidazole compound, an onium salt compound, a trihalomethyl compound, and a metallocene compound, and particularly preferably a hexaarylbiimidazole compound.
  • the polymerization initiators can be appropriately used in combination of two or more kinds thereof.
  • Examples of the hexaarylbiimidazole compound include the lophine dimers described in European Patent No. 24,629 , European Patent No. 10,7792 , and US Patent No. 4,410,621 ; for example, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimid
  • hexaarylbiimidazole compound in combination with a sensitizing colorant having a maximum absorption at from 300 nm to 450 nm.
  • a sulfonium salt, an iodonium salt, and a diazonium salt are preferably used.
  • a diaryliodonium salt and a triarylsulfonium salt are preferably used.
  • the onium salt compound in combination with an infrared absorber having a maximum absorption at from 750 nm to 1400 nm.
  • the polymerization initiators described in paragraphs [0071] to [0129] of JP-A No. 2007-206217 can be preferably used.
  • the polymerization initiators are suitably used singly or in combination of two or more kinds thereof.
  • the amount of use of the polymerization initiator in the image recording layer is preferably from 0.01% to 20% by mass, more preferably from 0.1% to 15% by mass, and still more preferably from 1.0% by mass to 10% by mass, with respect to the total solid content of the image recording layer.
  • total solid content means the total amount of components excluding the solvent, among all the components that constitute the image recording layer.
  • the polymerizable compound used in the image recording layer is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, and preferably two or more, terminal ethylenically unsaturated bonds. These are in the chemical form of, for example, a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof, and usually, a polymerizable monomer is used.
  • Examples of the monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), esters thereof, and amides thereof, and an ester between an unsaturated carboxylic acid and a polyhydric alcohol compound, or an amide between an unsaturated carboxylic acid and a polyvalent amine compound is preferably used.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid
  • esters thereof for example, acrylic acid, methacrylic acid, itaconic acid
  • an addition reaction product between an unsaturated carboxylic acid ester or amide, each having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group, and a monofunctional or polyfunctional isocyanate or an epoxy compound; and a dehydration condensation reaction product between such an unsaturated carboxylic acid ester or amide and a monofunctional or polyfunctional carboxylic acid, are also suitably used.
  • JP-A Japanese National-Phase Publication
  • JP-A No. 2006-508380 JP-A No. 2002-287344 , JP-A No. 2008-256850 , JP-A No. 2001-342222 , JP-A No. H09-179296 , JP-A No. H09-179297 , JP-A No. H09-179298 , JP-A No. 2004-294935 , JP-A No. 2006-243493 , JP-A No. 2002-275129 , JP-A No. 2003-64130 , JP-A No. 2003-280187 , and JP-ANo. H10-333321 .
  • the monomer of an ester between a polyhydric alcohol compound and an unsaturated carboxylic acid include, as acrylic acid esters, ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO)-modified triacrylate, and polyester acrylate oligomers.
  • acrylic acid esters ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythr
  • methacrylic acid esters examples include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, and bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane.
  • the monomer of an amide between a polyvalent amine compound and an unsaturated carboxylic acid include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
  • a urethane-based addition polymerizable compound produced using an addition reaction between an isocyanate group and a hydroxyl group is also suitable, and specific examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule, which is obtained by adding a vinyl monomer containing a hydroxyl group represented by the following Formula (A), to a polyisocyanate compound having two or more isocyanate groups in one molecule, as described in Japanese Patent Publication ( JP-B) No. S48-41708 .
  • CH 2 C(R 4 )COOCH 2 CH(R 5 )OH (A) provided that each of R 4 and R 5 represents H or CH 3 .
  • urethane acrylates described in JP-ANo. S51-37193 , JP-B No. H02-32293 , JP-B No. H02-16765 , JP-A No. 2003-344997 , and JP-A No. 2006-65210 ; urethane compounds having an ethylene oxide-based skeleton, described in JP-B No. S58-49860 , JP-B No. S56-17654 , JP-B No. S62-39417 , JP-B No. S62-39418 , JP-A No. 2000-250211 , and JP-A No. 2007-94138 ; and urethane compounds having hydrophilic groups, described in US Patent No. 7,153,632 , JP-A No. H08-505958 , JP-A No. 2007-293221 , and JP-A No. 2007-293223 , are also suitable.
  • a polymerizable compound capable of photooxidation as described in JP-A No. 2007-506125 is also suitable, and a polymerizable compound containing at least one urea group and/or tertiary amino group is particularly preferred. Specific examples include compounds described below.
  • the details of the structure of the polymerizable compound, single use or combined use, the method of use such as the amount of addition can be arbitrarily set in accordance with the final performance design of the photosensitive planographic printing plate precursor.
  • the polymerizable compound is used in an amount in the range of preferably from 5% to 75% by mass, more preferably from 25% to 70% by mass, and particularly preferably from 30% to 60% by mass, with respect to the total solid content of the image recording layer.
  • the image recording layer contains a sensitizing colorant.
  • Any sensitizing colorant can be used without any particular limitations as long as the sensitizing colorant absorbs light at the time of image exposure to enter an excited state, donates energy to the polymerization initiator through electron transfer, energy transfer, heat generation or the like, and enhances the polymerization initiation function.
  • a sensitizing colorant having a maximum absorption at 300 nm to 450 nm or 750 nm to 1400 nm is preferably used.
  • Examples of the sensitizing colorant having a maximum absorption in a wavelength range of 300 nm to 450 nm include merocyanines, benzopyrans, coumarins, aromatic ketones, anthracenes, styryls, and oxazoles.
  • the sensitizing colorants having maximum absorptions in a wavelength range of from 300 nm to 450 nm
  • more preferred examples of the colorant from the viewpoint of high sensitivity include a colorant represented by the following Formula (IX):
  • A represents an aryl group or heteroaryl group which may have a substituent;
  • R 1 , R 2 , and R 3 independently represents a monovalent non-metal atomic group, and is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.
  • Examples of the aryl group or heteroaryl group which may have a substituent, as represented by A in Formula (IX), are the same as the substituted or unsubstituted aryl groups and the substituted or unsubstituted heteroaryl groups described for R 1 , R 2 , and R 3 , respectively.
  • Such a sensitizing colorant that may be preferably used include the compounds described in paragraphs [0047] to [0053] of JP-A No. 2007-58170 , paragraphs [0036] to [0037] of JP-A No. 2007-93866 , and paragraphs [0042] to [0047] of JP-A No. 2007-72816 .
  • JP-A No. 2006-189604 JP-A No. 2007-171406
  • JP-A No. 2007-206216 JP-A No. 2007-206217
  • JP-A No. 2007-225701 JP-A No. 2007-225702
  • JP-A No. 2007-316582 JP-A No. 2007-328243
  • JP-A No. 2007-328243 can also be preferably used.
  • the sensitizing colorant having a maximum absorption at 750 nm to 1400 nm (hereinafter, also referred to as "infrared absorber”) will be described.
  • the infrared absorber a dye or a pigment is preferably used.
  • dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes.
  • cyanine dyes particularly preferred examples include cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes.
  • cyanine dyes or indolenine cyanine dyes are preferred, and particularly preferred examples include a cyanine dye represented by the following Formula (a):
  • X 1 represents a hydrogen atom, a halogen atom, -NPh 2 , -X 2 -L 1 , or a group shown below.
  • X 2 represents an oxygen atom, a nitrogen atom, or a sulfur atom
  • L 1 represents a hydrocarbon group having from 1 to 12 carbon atoms, an aryl group having a heteroatom (N, S, O, halogen atom, or Se), or a hydrocarbon group having from 1 to 12 carbon atoms and containing a heteroatom.
  • X a - has the same definition as Z a - that will be described below, and R a represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group, and a halogen atom.
  • R 1 and R 2 independently represents a hydrocarbon group having from 1 to 12 carbon atoms.
  • R 1 and R 2 are preferably hydrocarbon groups each having two or more carbon atoms.
  • R 1 and R 2 may also be linked to each other and form a ring, and when they form a ring, it is particularly preferable that they form a 5-membered ring or a 6-membered ring.
  • Ar 1 and Ar 2 may be identical with or different from each other, and each represents an aryl group which may have a substituent.
  • Preferred examples of the aryl group include a benzene ring and a naphthalene ring.
  • preferred examples of the substituent include a hydrocarbon group having 12 or fewer carbon atoms, a halogen atom, and an alkoxy group having 12 or fewer carbon atoms.
  • Y 1 and Y 2 may be identical with or different from each other, and each represents a sulfur atom, or a dialkylmethylene group having 12 or fewer carbon atoms.
  • R 3 and R 4 may be identical with or different from each other, and each represents a hydrocarbon group having 20 or fewer carbon atoms which may have a substituent.
  • Preferred examples of the substituent include an alkoxy group having 12 or fewer carbon atoms, a carboxyl group, and a sulfo group.
  • R 5 , R 6 , R 7 , and R 8 may be identical with or different from each other, and each represents a hydrogen atom, or a hydrocarbon group having 12 or fewer carbon atoms. In view of the availability of the raw material, it is preferably a hydrogen atom.
  • Z a - represents a counter anion.
  • Z a - is not necessary.
  • Preferred examples of Z a - include, from the viewpoint of storage stability of the image recording layer coating liquid, a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and particularly preferred examples include a perchlorate ion, a hexafluorophosphate ion, and an arylsulfonate ion.
  • Specific examples of the cyanine dye represented by Formula (a) that can be suitably used include the compounds described in paragraphs [0017] to [0019] of JP-A No. 2001-133969 , paragraphs [0016] to [0021] of JP-A No. 2002-023360 , and paragraphs [0012] to [0037] of JP-A No. 2002-040638 ; preferred examples include the compounds described in paragraphs [0034] to [0041] of JP-A No. 2002-278057 , and paragraphs [0080] to [0086] of JP-A No. 2008-195018 ; and particularly preferred examples include the compounds described in paragraphs [0035] to [0043] of JP-A No. 2007-90850 .
  • the infrared absorbing dyes may be used singly or in combination of two or more kinds thereof, and an infrared absorber other than an infrared absorbing dye, such as a pigment, may also be used in combination.
  • an infrared absorber other than an infrared absorbing dye, such as a pigment may also be used in combination.
  • Preferred examples of the pigment include the compounds described in paragraphs [0072] to [0076] of JP-A No. 2008-195018 .
  • a preferred amount of addition of the sensitizing colorant is preferably from 0.05 parts to 30 parts by mass, more preferably from 0.1 parts to 20 parts by mass, and particularly preferably from 0.2 parts to 10 parts by mass, with respect to 100 parts by mass of the total solid content of the image recording layer.
  • the image recording layer may contain a binder polymer.
  • the binder polymer use is made of a polymer which can support the image recording layer components on a support and can be removed by a developer liquid.
  • the binder polymer that may be used include a (meth)acrylic polymer, a polyurethane resin, a polyvinyl alcohol resin, a polyvinyl butyral resin, a polyvinyl formal resin, a polyamide resin, a polyester resin, and an epoxy resin.
  • a (meth)acrylic polymer, a polyurethane resin, and a polyvinyl butyral resin are preferably used.
  • a "(meth)acrylic polymer” refers to a copolymer having a (meth)acrylic acid derivative such as (meth)acrylic acid, a (meth)acrylic acid ester (an alkyl ester, an aryl ester, an allyl ester, or the like), (meth)acrylamide, or a (meth)acrylamide derivative, as a polymerization component.
  • a "polyurethane resin” refers to a polymer produced by a condensation reaction between a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups.
  • a "polyvinyl butyral resin” refers to a polymer synthesized by allowing a polyvinyl alcohol that is obtained by partially or fully saponifying polyvinyl acetate, to react with butyl aldehyde under acidic conditions (acetalization reaction), and also includes a polymer in which an acid group or the like has been introduced by a method of allowing residual hydroxyl groups to react with a compound having an acid group or the like.
  • a suitable example of the (meth)acrylic polymer according to the invention may be a copolymer having a repeating unit containing an acid group.
  • the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, but particularly, a carboxylic acid group is preferred.
  • a repeating unit containing an acid group a repeating unit derived from (meth)acrylic acid, or a repeating unit represented by the following Formula (i) is preferably used.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a single bond or a linking group having a valence of n+1
  • A represents an oxygen atom or -NR 3 -
  • R 3 represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 10 carbon atoms
  • n represents an integer from 1 to 5.
  • the linking group represented by R 2 in Formula (i) is composed of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms is preferably from 1 to 80.
  • the proportion (mol%) of the copolymerization component having a carboxylic acid group among all the copolymerization components of the (meth)acrylic polymer is preferably from 1% to 70% from the viewpoint of developability. When a balance between developability and printing durability is considered, the proportion is more preferably 1% to 50%, and particularly preferably from 1% to 30%.
  • binder polymers are described in paragraphs [0018] to [0127] of JP-A No. 2004-318053 , and the compounds described herein are suitably used as binder polymers in this invention.
  • the (meth)acrylic polymer used as a binder polymer may further have a crosslinkable group.
  • the crosslinkable group is not particular limited as long as it is a group capable of crosslinking a polymer during the course of a radical polymerization reaction occurring in the image recording layer when the photosensitive planographic printing plate precursor is exposed, and examples of the functional group capable of addition polymerization reaction include an ethylenically unsaturated bond group, an amino group, and an epoxy group.
  • the crosslinkable group may also be a functional group which can be converted to a radical by light irradiation, and examples of such a crosslinkable group include a thiol group and a halogen group.
  • an ethylenically unsaturated bond group is preferred.
  • the ethylenically unsaturated bond group is preferably a styryl group, a (meth)acryloyl group, or an allyl group.
  • the content of the crosslinkable group in the (meth)acrylic polymer is preferably from 0.01 mmol to 10.0 mmol, and more preferably from 0.05 mmol to 9.0 mmol, and particularly preferably from 0.1 mmol to 8.0 mmol, per gram of the polymer.
  • Suitable examples of the polyurethane resin used as the binder polymer according to the invention include the polyurethane resins described in paragraphs [0099] to [0210] of JP-A No. 2007-187836 , paragraphs [0019] to [0100] of JP-A No. 2008-276155 , paragraphs [0018] to [0107] of JP-ANo. 2005-250438 , and paragraphs [0021] to [0083] of JP-ANo. 2005-250158 .
  • Suitable examples of the polyvinyl butyral resin used as the binder polymer in the invention include the polyvinyl butyral resins described in paragraphs [0006] to [0013] of JP-A No. 2001-75279 .
  • a portion of the acid groups in the binder polymer may be neutralized with a basic compound.
  • the basic compound include a compound containing basic nitrogen, alkali metal hydroxides, and quaternary ammonium salts of alkali metals.
  • the binder polymer preferably has a mass average molecular weight of 5000 or more, and more preferably from 10,000 to 300,000, and preferably has a number average molecular weight of 1000 or more, and more preferably from 2000 to 250,000.
  • the dispersity is preferably from 1.1 to 10.
  • the binder polymers may be used singly, or may be used as a mixture of two or more kinds.
  • the content of the binder polymer is preferably from 5% to 75% by mass, more preferably from 10% to 70% by mass, and still more preferably from 10% to 60% by mass, with respect to the total solid content of the image recording layer.
  • the total content of the polymerizable compound and the binder polymer is preferably 90% by mass or less with respect to the total solid content of the image recording layer. If the total content is more than 90% by mass, a decrease in sensitivity and a decrease in developability may occur. The total content is more preferably from 35% to 80% by mass.
  • the image recording layer contains a chain transfer agent.
  • the chain transfer agent is defined in, for example, Kobunshi Jiten (Polymer Dictionary), 3rd Edition (edited by the Society of Polymer Science, Japan, 2005), pp. 683 to 684 .
  • the chain transfer agent for example, a group of compounds having SH, PH, SiH or GeH in the molecule are used. These can produce a radical by donating hydrogen to a less active radical species, or can produce a radical by being oxidized and then deprotonated.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, and 5-mercaptotetrazoles
  • 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, and 5-mercaptotetrazoles can be particularly preferably used.
  • the amount of addition of the chain transfer agent is preferably from 0.01 parts to 20 parts by mass, more preferably from 1 part to 10 parts by mass, and particularly preferably from 1 part to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the image recording layer.
  • various additives can be further incorporated if necessary.
  • the additives include a surfactant for promoting developability and enhancing the coated surface state; microcapsules for achieving a balance between developability and printing durability; a hydrophilic polymer for enhancing developability or enhancing dispersion stability of microcapsules; a colorant or a printing agent for visualizing image areas and non-image areas; a polymerization inhibitor for preventing unnecessary thermal polymerization of the radical polymerizable compound during production of the image recording layer or during storage; a hydrophobic low molecular weight compound such as a higher fat derivative for preventing polymerization inhibition by oxygen; inorganic fine particles or organic fine particles for increasing the cured film strength of the image areas; a hydrophilic low molecular weight compound for enhancing developability; a co-sensitizer for enhancing sensitivity; and a plasticizer for enhancing plasticity.
  • the image recording layer is formed by dispersing or dissolving the various necessary components described above in a solvent to prepare a coating liquid, and applying the coating liquid.
  • a solvent examples include, but are not limited to, methyl ethyl ketone, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and ⁇ -butyrolactone.
  • the solvents may be used singly or as mixtures.
  • the solid content concentration of the coating liquid is preferably from 1% to 50% by mass.
  • the amount of coating (solid content) of the image recording layer obtainable after coating and drying is preferably from 0.3 g/m 2 to 3.0 g/m 2 .
  • Various methods can be used for the coating. Examples include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.
  • the photosensitive planographic printing plate precursor according to the invention is provided with a protective layer (oxygen blocking layer) on the image recording layer, in order to block diffusion and penetration of oxygen that impedes the polymerization reaction at the time of exposure.
  • a protective layer oxygen blocking layer
  • any of a water-soluble polymer and a water-insoluble polymer can be appropriately selected and used, and if necessary, a mixture of two or more kinds can be used.
  • Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinylpyrrolidone, a water-soluble cellulose derivative, and poly(meth)acrylonitrile.
  • a water-soluble polymer having relatively excellent crystallinity it is preferable to use a water-soluble polymer having relatively excellent crystallinity, and specifically, when polyvinyl alcohol is used as a main component, the most favorable results are obtained in terms of fundamental characteristics such as oxygen blocking properties and development removability.
  • the polyvinyl alcohol used in the protective layer may be partially substituted with an ester, an ether or an acetal, as long as the polyvinyl alcohol contains unsubstituted vinyl alcohol units for having the necessary oxygen blocking properties and water-solubility. Similarly, the polyvinyl alcohol may also partially have other copolymerization components.
  • Polyvinyl alcohol may be obtained by hydrolyzing polyvinyl acetate, and a specific example of the polyvinyl alcohol may be a polyvinyl alcohol having a degree of hydrolysis of from 69.0 mol% to 100 mol% and a number of polymerization repeating units in the range of from 300 to 2400. Specific examples include the compounds described in paragraphs [0233] to [0234] of JP-A No. 2004-318053 .
  • the percentage content of the polyvinyl alcohol in the protective layer is preferably from 20% to 95% by mass, and more preferably from 30% to 90% by mass.
  • any known modified polyvinyl alcohol can also be preferably used.
  • an acid-modified polyvinyl alcohol having a carboxylic acid group or a sulfonic acid group is preferably used.
  • suitable examples include the polyvinyl alcohols described in JP-ANo. 2005-250216 and JP-ANo. 2006-259137 .
  • the component to be mixed therewith is preferably a modified polyvinyl alcohol, polyvinylpyrrolidone, or a modification product thereof, from the viewpoints of oxygen blocking properties and development removability.
  • the content thereof in the protective layer is from 3.5% to 80% by mass, preferably from 10% to 60% by mass, and more preferably from 15% to 30% by mass.
  • an inorganic layered compound into the protective layer, for the purpose of enhancing the oxygen blocking properties or the image recording layer surface protectiveness.
  • fluorine-containing swellable synthetic mica which is a synthetic inorganic layered compound is particularly useful.
  • suitable examples include inorganic layered compounds described in JP-ANo. 2005-119273 .
  • the amount of coating of the protective layer is preferably 0.05 g/m 2 to 10 g/m 2 as the amount of coating after drying, and when the protective layer contains an inorganic layered compound, the amount of coating is more preferably from 0.1 g/m 2 to 5 g/m 2 , while when the protective layer does not contain an inorganic layered compound, the amount of coating is more preferably from 0.5 g/m 2 to 5 g/m 2 .
  • the support that is used in the photosensitive planographic printing plate precursor is not particularly limited, and a plate-shaped hydrophilic support which is dimensionally stable is acceptable.
  • an aluminum plate is preferred.
  • a surface treatment such as a surface roughening treatment or an anodization treatment.
  • the surface roughening treatment of the aluminum plate surface is carried out by various methods, and examples include a mechanical surface roughening treatment, an electrochemical surface roughening treatment (surface roughening treatment of dissolving the surface electrochemically), and a chemical surface roughening treatment (surface roughening treatment of selectively dissolving the surface chemically).
  • the methods described in paragraphs [0241] to [0245] of JP-ANo. 2007-206217 can be preferably used.
  • the support preferably has a center line average roughness of from 0.10 ⁇ m to 1.2 ⁇ m. In this range, favorable adhesiveness to the image recording layer, favorable printing durability, and favorable uncontaminability are obtained.
  • the color density of the support is preferably from 0.15 to 0.65 as a reflection density value. With this range, favorable image formability caused by the prevention of halation at the time of image exposure, and favorable plate inspectability after development, are obtained.
  • the thickness of the support is preferably from 0.1 mm to 0.6 mm, and more preferably from 0.15 mm to 0.4 mm.
  • the photosensitive planographic printing plate precursor in order to enhance hydrophilicity of non-image areas and to prevent print contamination, it is also suitable to perform a hydrophilization treatment of the support surface, or to provide an undercoat layer between the support and the image recording layer.
  • hydrophilization treatment of the support surface examples include an alkali metal silicate treatment method of subjecting the support to an immersion treatment in an aqueous solution of sodium silicate or the like, or to an electrolytic treatment; a method of treating the support with potassium fluorozirconate; and a method of treating the support with polyvinylphosphonic acid.
  • a method of subjecting the support to an immersion treatment in an aqueous solution of polyvinylphosphonic acid is preferably used.
  • an undercoat layer including a compound having an acidic group such as phosphonic acid, phosphoric acid or sulfonic acid
  • these compounds preferably further contain polymerizable groups in order to increase the adhesiveness to the image recording layer.
  • the polymerizable group is preferably an ethylenically unsaturated bond group.
  • a compound having a hydrophilicity imparting group such as an ethyleneoxy group may also be listed as a suitable compound.
  • These compounds may be low molecular weight compounds, or may be high molecular weight polymers. These compounds may be used in combination of two or more kinds thereof if necessary.
  • Suitable examples include a silane coupling agent having an addition polymerizable ethylenically unsaturated bond group described in JP-ANo. H10-282679; and a phosphorus compound having an ethylenically unsaturated bond group described in JP-ANo. H02-304441.
  • Undercoat layers containing lower molecular weight or high molecular weight compounds having a crosslinkable group (preferably, an ethylenically unsaturated bond group), a functional group that interacts with the support surface, and a hydrophilic group as described in JP-ANo. 2005-238816 , JP-ANo. 2005-125749 , JP-ANo. 2006-239867 , and JP-ANo. 2006-215263 are also preferably used.
  • the undercoat layer is applied by a known method.
  • the amount of coating (solid content) of the undercoat layer is preferably from 0.1 mg/m 2 to 100 mg/m 2 , and more preferably from 1 mg/m 2 to 40 mg/m 2 .
  • a back coat can be provided on the back surface of the support (surface on the opposite side from the image recording layer).
  • Suitable examples of the back coat include a layer formed from the organic polymer compound described in JP-ANo. H05-45885; and a coating layer formed from a metal oxide obtainable by hydrolysis and polycondensation of an organometallic compound or an inorganic metal compound described in JP-ANo. H06-35174.
  • an alkoxy compound of silicon such as Si(OCH 3 ) 4 , Si(OC 2 H 5 ) 4 , Si(OC 3 H 7 ) 4 , or Si(OC 4 H 9 ) 4 , from the viewpoint that the raw materials are available at low cost.
  • a planographic printing plate is produced by subjecting the photosensitive planographic printing plate precursor according to the invention to imagewise exposure and development processing.
  • a development process and a desensitization process are simultaneously carried out using a developer liquid in a single development processing bath of an automatic developing machine.
  • the photosensitive planographic printing plate precursor is imagewise exposed by laser exposing through a transparent original image having a line image, a halftone image and the like, or by laser light scanning based on digital data.
  • the wavelength of the light source is preferably from 300 nm to 450 nm, or from 750 nm to 1400 nm.
  • a photosensitive planographic printing plate precursor including a sensitizing colorant having a maximum absorption in this region in the image recording layer is used
  • a photosensitive planographic printing plate precursor containing an infrared absorber which is a sensitizing colorant having absorption in this region is used.
  • semiconductor lasers are suitable.
  • solid lasers and semiconductor lasers that emit infrared radiation are suitable.
  • the exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.
  • the developer liquid described above can be used as a developer liquid and developer replenishing liquid for exposed photosensitive planographic printing plate precursors, and it is preferable to apply the developer liquid to a developing bath of an automatic processing machine as described above.
  • the processing ability may be restored by using a replenishing liquid or a fresh developer liquid.
  • This replenishing system is preferably applied also to the recycling method of the invention.
  • Development processing can be carried out suitably by an automatic processing machine equipped with a means for supplying a developer liquid, and a scrubbing member.
  • a photosensitive planographic printing plate precursor when a protective layer containing the polyvinyl alcohol is provided on the image recording layer, a photosensitive planographic printing plate precursor can be subjected, after laser exposure, without going through a water washing step, to a development process for removing the protective layer and the image recording layer in unexposed areas, and a desensitization process of the surface of the image areas thus formed, in a single bath, using a developer liquid containing the particular surfactant described above and preferably having a pH of from 6 to 10.
  • a developer liquid containing the particular surfactant described above when compared with a conventional method of performing these processes in sequence as separate steps, the amount of the process waste liquid is further reduced.
  • the protective layer can be optionally removed by applying a water-washing process in advance, prior to the development process.
  • the protective layer and the image recording layer in unexposed areas are both removed, and the image areas thus formed is subjected to a desensitization process. Therefore, the planographic printing plate obtained after the development process can be immediately mounted on a printing machine and subjected to printing.
  • a development process and a desensitization process are carried out in a single bath by incorporating a particular surfactant into the developer liquid, a post-washing step with water is not particularly necessary, and a drying step can be carried out immediately. After the development process, it is preferable to perform drying after removing any excess developer liquid using a squeeze roller.
  • the automatic development processing machine 100 illustrated in Fig. 3 is composed of a chamber in which an external shape is formed by a frame 202, and includes a preheating (preheat) section 200, a development section 300, and a drying section 400 that are formed continuously along the conveyance direction (arrow A) of a conveyance path 11 for the photosensitive planographic printing plate precursor.
  • the preheating section 200 has a heating chamber 208 having an inlet port 212 and an outlet port 218, and disposed inside the heating chamber are skewer type rollers 210, a heater 214, and a circulating fan 216.
  • the development section 300 is separated from the preheating section 200 by an outer panel 310, and the outer panel 310 is provided with a slit-like insertion opening 312.
  • a processing tank 306 having a developing bath 308 filled with a developer liquid, and a pair of inserting rollers 304 that guide the photosensitive planographic printing plate precursor into the inside of the processing tank 306 are provided.
  • the top of the developing bath 308 is covered with a cover lid 324.
  • a guide roller 344, a guide member 342, a pair of in-liquid rollers 316, a pair of brush rollers 322, a pair of brush rollers 326, and a pair of export rollers 318 are provided in order from the upstream side of the conveyance direction.
  • the photosensitive planographic printing plate precursor conveyed to the inside of the developing bath 308 is passed through between the pairs of brush rollers 322 and 326 that rotate while being immersed in the developer liquid, and thereby non-image areas are removed.
  • the spray pipe 330 is connected with a pump (not shown in the diagram), and the developer liquid in the developing bath 308 that has been suctioned by the pump is spouted into the developing bath 308 from the spray pipe 330.
  • the side wall of the developing bath 308 is provided with an overflow opening 51 formed at the upper end of a first circulation pipe C1, and an excess amount of the developer liquid flows into the overflow opening 51, passes through the first circulation pipe C1, and is discharged to an external tank 50 provided outside the development section 300.
  • the external tank 50 is connected with a second circulation pipe C2, and a filter unit 54 and a developer liquid supplying pump 55 are provided in the second circulation pipe C2.
  • the developer liquid is supplied from the external tank 50 to the developing bath 308 by the developer liquid supplying pump 55.
  • an upper limit liquid level gauge 52 and a lower limit liquid level gauge 53 are provided inside the external tank 50.
  • the developing bath 308 is connected to a replenishing water tank 71 through a third circulation pipe C3.
  • a water replenishing pump 72 Provided in the third circulation pipe C3 is a water replenishing pump 72, and the water stored in the replenishing water tank 71 is supplied to the developing bath 308 by this water replenishing pump 72.
  • a liquid temperature sensor 336 is provided on the upstream side of the pair of in-liquid rollers 316, and a liquid level gauge 338 is provided on the upstream side of the pair of export rollers 318.
  • a slit-like insertion opening 334 is provided on a partition plate 332 that is disposed between the development section 300 and the drying section 400. Also, a shutter (not shown in the diagram) is provided in the pathway between the development section 300 and the drying section 400, and the pathway is closed by the shutter when the planographic printing plate does not pass through the pathway.
  • the drying section 400 includes a supporting roller 402, ducts 410 and 412, a pair of conveying rollers 406, ducts 410 and 412, and a pair of conveying rollers 408 provided therein in this order. Slit openings 414 are provided at the ends of the ducts 410 and 412. Also, the drying section 400 is provided with a drying means such as a hot air supplying means or a heat generating means (not shown in the diagram). The drying section 400 is provided with a discharge port 404, and the planographic printing plate dried by the drying means is discharged through the discharge port 404.
  • the "development initiating liquid” means an untreated developer liquid unless particularly stated otherwise, and the “developer replenishing liquid” means a replenishing liquid for development that is replenished into the developer liquid in the developing bath, which has been deteriorated as a result of the development process of the photosensitive planographic printing plate precursor, absorption of carbon dioxide, and the like.
  • composition of the developer replenishing liquid is basically the same composition as the composition of the development initiating liquid described above; however, if necessary, the developer replenishing liquid may be highly active compared with the development initiating liquid, in order to restore the activity of the deteriorated developer liquid.
  • the development initiating liquid that is initially fed into the developing bath of the automatic developing machine 10 is deteriorated by the eluted substance generated by the processing of the photosensitive planographic printing plate precursor. Therefore, in order to perform the development process continuously for a long time in the automatic developing machine 10, it is usually necessary to replenish, intermittently or continuously, at least any one of the developer replenishing liquid or water, which compensates for deterioration, in order to maintain the development quality of the photosensitive planographic printing plate precursor.
  • the following four patterns may be conceived: (1) replenishing with a developer liquid having the same concentration as that of the development initiating liquid that is initially introduced; (2) replenishing with a developer liquid having the same concentration as that of the development initiating liquid that is initially introduced, and water in an amount that corresponds to volatilization; (3) replenishing with a developer liquid with a higher concentration, and water; and (4) replenishing with water in an amount that corresponds to volatilization.
  • a concentrated developer liquid is diluted in advance with reclaimed water to obtain a developer liquid having the same concentration as that of the development initiating liquid that is initially introduced, and then this is used for replenishing.
  • replenishment of the developer liquid and replenishment of water are carried out independently, and reclaimed water is used for evaporation correction.
  • replenishment is carried out with reclaimed water only.
  • the entire surface may be heated if necessary, before exposure, during exposure, or at any time between exposure and development.
  • the image forming reaction in the image recording layer is accelerated, and there may be merits such as an enhancement of sensitivity or printing durability, or stabilization of sensitivity.
  • it is also effective to perform post-heating of the entire surface or exposure of the entire surface for the image obtained after development.
  • heating before development is preferably carried out under mild conditions of 150°C or lower. If the temperature is too high, there is a problem in that non-image areas may be fogged. Very harsh conditions are used for the heating after development.
  • the temperature is in the range of from 200°C to 500°C. If the temperature is low, a sufficient image reinforcing action is not obtained, and if the temperature is too high, there occur problems such as deterioration of the support, and thermal decomposition of image areas.
  • the aluminum plate In order to remove the rolling oil at the surface of an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, the aluminum plate was subjected to a degreasing treatment for 30 seconds at 50°C using a 10 mass% aqueous solution of sodium aluminate, subsequently the aluminum surface was grained using three bundled nylon brushes having a fiber diameter of 0.3 mm and an aqueous suspension of pumice (specific gravity: 1.1 g/cm 3 ) having a median diameter of 25 ⁇ m, and then the aluminum surface was washed thoroughly with water.
  • a degreasing treatment for 30 seconds at 50°C using a 10 mass% aqueous solution of sodium aluminate
  • the aluminum surface was grained using three bundled nylon brushes having a fiber diameter of 0.3 mm and an aqueous suspension of pumice (specific gravity: 1.1 g/cm 3 ) having a median diameter of 25 ⁇ m, and then the aluminum surface was
  • This plate was etched by immersing the plate in a 25 mass% aqueous solution of sodium hydroxide at 45°C for 9 seconds, washed with water, subsequently further immersed in a 20 mass% aqueous solution of nitric acid at 60°C for 20 seconds, and washed with water.
  • the amount of etching of the grained surface at this time was about 3 g/m 2 .
  • an electrochemical surface roughening treatment was carried out continuously using an alternating current voltage of 60 Hz.
  • the electrolyte liquid used at this time was a 1 mass% aqueous nitric acid solution (containing 0.5% by mass of aluminum ions) having a liquid temperature of 50°C.
  • a trapezoidal rectangular wave alternating current having a time TP which was taken by the current value to reach from zero to the peak value, of 0.8 msec and having a duty ratio of 1:1 was used, and the electrochemical surface roughening treatment was carried out using a carbon electrode as a counter electrode. Ferrite was used for an auxiliary anode.
  • the current density was 30 A/dm 2 as the peak value of current, and 5% of the current flowing from the power supply was distributed to the auxiliary anode.
  • the amount of electricity used for the nitric acid electrolysis the amount of electricity when the aluminum plate was the anode was 175 C/dm 2 . Thereafter, the aluminum plate was washed with water by spraying.
  • an electrochemical surface roughening treatment was carried out using an electrolyte liquid that was a 0.5 mass% aqueous hydrochloric acid solution (containing 0.5% by mass of aluminum ions) having a liquid temperature of 50°C, by the same method as the nitric acid electrolysis, under the conditions that the amount of electricity when the aluminum plate was the anode was 50 C/dm 2 . Thereafter, the aluminum plate was washed with water by spraying.
  • a direct current anodic oxide film of 2.5 g/m 2 was provided using a 15 mass% aqueous sulfuric acid solution (containing 0.5% by mass of aluminum ions) as an electrolyte liquid under the conditions of a current density of 15 A/dm 2 , and then the aluminum plate was washed with water and dried. Thus, an aluminum support 1 was produced.
  • the center line average roughness (Ra) of the support obtained in this manner was measured using a needle having a diameter of 2 ⁇ m, and the roughness was 0.51 ⁇ m.
  • the aluminum support 1 was treated with a 1 mass% aqueous solution of sodium silicate for 10 seconds at 20°C, and thus an aluminum support 2 was produced.
  • the surface roughness thereof was measured, and the value was 0.54 ⁇ m (Ra expression according to JIS B0601).
  • An undercoat layer coating liquid (1) as described below was applied on the aluminum support 2 using a bar coater, and was dried at 80°C for 20 seconds. Thus, a support 3 was produced. The mass of coating of the undercoat layer after drying was 15 mg/m 2 .
  • An image recording layer coating liquid 1 having a composition as described below was applied by bar coating on the undercoat layer of the support 3, and was dried in an oven at 90°C for 60 seconds. Thus, an image recording layer 1 having a dried amount of coating of 1.3 g/m 2 was formed.
  • a protective layer coating liquid 1 having a composition as described below was applied on the image recording layer 1 using a bar such that the dried amount of coating would be 1.5 g/m 2 , and then the coating liquid was dried at 125°C for 70 seconds to form a protective layer.
  • a photosensitive planographic printing plate precursor 1 was obtained.
  • the photosensitive planographic printing plate precursor 1 was imagewise exposed using a Violet semiconductor laser plate setter Vx9600 (equipped with an InGaN-based semiconductor laser (emission wavelength: 405 nm ⁇ 10 nm/power output: 30 mW)) manufactured by Fujifilm Electronic Imaging, Ltd. (FFEI).
  • the imagewise exposure was carried out at a resolution of 2438 dpi using an FM screen (TAFFETA 20) manufactured by Fujifilm Corp., at an amount of plate surface exposure of 0.05 mJ/cm 2 so as to obtain a halftone area ratio of 50%.
  • preheating was carried out at 100°C for 30 seconds.
  • the photosensitive planographic printing plate precursor after exposure was subjected to a development process using an automatic development processing machine having a structure illustrated in Fig. 3 , and using various developer liquids described below.
  • the automatic development processing machine had a brush roll having an outer diameter of 50 mm and produced by planting polybutylene terephthalate fibers (diameter of fiber: 200 ⁇ m, fiber length: 17 mm), and the brush roll was rotated 200 times per minute (circumferential speed of the edge of the brush: 0.52 m/sec) in the same direction as the conveyance direction.
  • the temperature of the developer liquid was 30°C.
  • the conveyance of the photosensitive planographic printing plate precursor was carried out at a conveyance speed of 100 cm/min. After the development process, drying was carried out at the drying section. The drying temperature was 80°C.
  • Surfactants (R-1) and (R-2) are comparative surfactants that do not have a phenyl group or a naphthyl group.
  • the water vapor evaporatively separated in the waste liquid concentrating apparatus XR-2000 manufactured by Fujifilm Global Graphic Systems Co., Ltd. was condensed, and reclaimed water was obtained.
  • any reclaimed water that did not cause any problem in the evaluations described above was used.
  • the reclaimed water was supplied to a replenishing water tank, and a required amount was circulated through the replenishing water tank to the developing bath of the automatic developing machine.
  • An aluminum plate (material: 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5 mass% aqueous solution of sodium hydroxide maintained at 65°C, and the aluminum plate was subjected to a degreasing treatment for one minute and then washed with water. This aluminum plate was immersed for one minute in a 10 mass% aqueous hydrochloric acid solution maintained at 25°C to be neutralized, and then was washed with water.
  • this aluminum plate was subjected to an electrolytic surface roughening for 60 seconds in a 0.3 mass% aqueous hydrochloric acid solution using an alternating current under the conditions of 25°C and a current density of 100 A/dm 2 , and then the aluminum plate was subjected to a desmutting treatment for 10 seconds in a 5 mass% aqueous solution of sodium hydroxide maintained at 60°C.
  • This aluminum plate was subjected to an anodization treatment for one minute in a 15 mass% aqueous sulfuric acid solution under the conditions of 25°C, a current density of 10 A/dm 2 , and a voltage of 15 V, further immersed in a 1 mass% aqueous solution of polyvinylphosphonic acid at 60°C for 10 seconds, washed with hard water having a calcium ion concentration of 75 ppm at 20°C for 4 seconds, and washed with pure water for 4 seconds, thereby carrying out a hydrophilization treatment, and was dried.
  • a support 4 was produced.
  • the amount of calcium attached was 2.0 mg/m 2 .
  • the surface roughness of the support 4 was measured, and the value was 0.44 ⁇ m (indication of Ra according to JIS B0601).
  • An image recording layer coating liquid (2) having the composition described below was applied on a support 4 by bar coating, and then the coating liquid was dried in an oven at 90°C for 60 seconds. Thus, an image recording layer 2 having an amount of dried coating of 1.3 g/m 2 was formed.
  • a protective layer coating liquid 2 having the following composition was applied on the image recording layer 2 by bar coating such that the amount of dried coating would be 1.2 g/m 2 , and then the coating liquid was dried at 125°C for 70 seconds to form a protective layer 2.
  • a photosensitive planographic printing plate precursor 2 was obtained.
  • Surfactant (R-3) is a comparative surfactant that does not have a phenyl group or naphthyl group.
  • a photosensitive planographic printing plate precursor after exposure was subjected to a development process using an automatic development processing machine having a structure illustrated in Fig. 3 , and using the various developer liquids described in the following Table 3.
  • the automatic development processing machine had a brush roll having an outer diameter of 50 mm and produced by planting polybutylene terephthalate fibers (diameter of fiber: 200 ⁇ m, fiber length: 17 mm), and the brush roll was rotated 200 times per minute (circumferential speed of the edge of the brush: 0.52 m/sec) in the same direction as the conveyance direction.
  • the temperature of the developer liquid was 30°C.
  • the conveyance of the photosensitive planographic printing plate precursor was carried out at a conveyance speed of 100 cm/min.
  • a continuous plate-making process of a photosensitive planographic printing plate precursor, a waste liquid concentrating step, and a reclaimed water producing step were carried out in the same manner as in Example 1, except that the developer liquids of Invented Products 14 to 22 and Comparative Products 9 to 14 described in the above Table 3 were used instead of Invented Product 1 as the developer liquid, and the photosensitive planographic printing plate precursor 2 was used instead of the photosensitive planographic printing plate precursor 1.
  • Table 4 The results obtained by performing evaluations in the same manner are presented in the following Table 4.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (10)

  1. Verfahren zum Konzentrieren von Abfallflüssigkeit von einem Plattenerzeugungsverfahren einer Flachdruckplatte, wobei das Verfahren enthält:
    einen Plattenerzeugungs-Verarbeitungsschritt zum gleichzeitigen Durchführen eines Entwicklungsverfahrens und eines Desensibilisierungsverfahrens bei einem lichtempfindlichen Flachdruckplattenvorläufer vom Negativtyp, bei dem eine radikalisch polymerisierbare Bildaufzeichnungsschicht auf einem Träger vorliegt, nach Belichtung unter Verwendung einer Entwicklerflüssigkeit in einem einzelnen Entwicklungsverarbeitungsbad einer automatischen Entwicklungsmaschine, die den lichtempfindlichen Flachdruckplattenvorläufer vom Negativtyp nach Belichtung entwickelt,
    worin die Entwicklerflüssigkeit von 1 bis 10 Masse-%, bezogen auf die Gesamtmenge der Entwicklerflüssigkeit, eines Tensides mit einer Phenylgruppe oder einer Naphthylgruppe und zumindest einer Ethylenoxidgruppe oder einer Propylenoxidgruppe enthält,
    und einen Gehalt eines organischen Lösungsmittels mit einem Siedepunkt in einem Bereich von 100 bis 300°C von 2 Masse-% oder weniger hat, bezogen auf die Gesamtmenge der Entwicklerflüssigkeit, und
    im Wesentlichen kein organisches Lösungsmittel mit einem Siedepunkt von weniger als 100°C oder mehr als 300°C aufweist,
    einen Abfallflüssigkeits-Konzentrationsschritt zum verdampfenden Konzentrieren der Plattenerzeugungsverfahren-Abfallflüssigkeit, erzeugt durch den Plattenerzeugungsverarbeitungsschritt unter Verwendung einer Abfallflüssigkeit-Konzentrationsanlage, so dass ein Verhältnis eines Volumen der Plattenerzeugungsverfahren-Abfallflüssigkeit nach Konzentration zu einem Volumen der Plattenerzeugungsverfahren-Abfallflüssigkeit vor der Konzentration von 1/2 bis 1/10 ist, und
    einen Wiedergewinnungswasser-Erzeugungsschritt zum Erzeugen von wiedergewonnenem Wasser durch Kondensieren von Wasserdampf, der in dem Abfallflüssigkeit-Konzentrationsschritt getrennt ist,
    worin ein pH der Entwicklerflüssigkeit von 6 bis 10 ist, worin eine Entwicklerflüssigkeit ausgeschlossen ist, die ein Tensid und ein Hydroxid eines Alkalimetalls enthält, aber keine Silikatverbindung enthält und die einen pH von 10 hat.
  2. Verfahren zum Recyceln von Abfallflüssigkeit von einem Plattenerzeugungsverfahren einer Flachdruckplatte, wobei das Verfahren nach den Schritten gemäß Anspruch 1 enthält:
    einen Zuführschritt für wiedergewonnenes Wasser zum Zuführen des wiedergewonnenen Wassers, erhalten in dem Erzeugungsschritt für wiedergewonnenes Wasser, zu der automatischen Entwicklungsmaschine.
  3. Verfahren gemäß Anspruch 2, worin in dem Tensid die Zahl der Ethylenoxidgruppen oder Propylenoxidgruppen von 5 bis 30 ist.
  4. Verfahren gemäß Anspruch 2 oder 3, worin die Entwicklerflüssigkeit weiterhin zumindest eine Verbindung enthält, dargestellt durch die folgende Formel (1), Formel (2) oder Formel (3), und ein Gesamtgehalt der Verbindungen, dargestellt durch die folgenden Formeln (1), (2) und (3) in der Entwicklerflüssigkeit weniger als 20 Masse-% ist:
    Figure imgb0134
     worin in der Formel (1) R1 ein Wasserstoffatom, eine Alkylgruppe oder ein Substituent mit der folgenden Struktur ist:
    Figure imgb0135
     worin R8 ein Wasserstoffatom oder eine Alkylgruppe ist und
    A ein Wasserstoffatom, Alkylgruppe, monovalenter Substituent mit einer Ethylenoxidgruppe, monovalenter Substituent mit einer Carbonsäuregruppe oder monovalenter Substituent mit einem Carbonsäuresalz ist, und B ein monovalenter Substituent mit einer Ethylenoxidgruppe, monovalenter Substituent mit einer Carbonsäuregruppe oder monovalenter Substituent mit einem Carbonsäuresalz ist,
    Figure imgb0136
     worin in der Formel (2) R2 und R3 jeweils unabhängig ein Wasserstoffatom oder eine Alkylgruppe sind, die einen Substituenten haben kann, aber zumindest eines von R2 oder R3 eine Alkylgruppe ist, die einen Substituenten haben kann, D eine Alkylgruppe oder ein monovalenter Substituent mit einer Ethylenoxidgruppe ist und E ein monovalenter Substituent mit einem Carboxylatanion oder ein monovalenter Substituent mit einem Oxidanion (O-) ist, und
    Figure imgb0137
     worin in der Formel (3) R4, R5, R6 und R7 jeweils unabhängig ein Wasserstoffatom oder eine Alkylgruppe sind und Z- ein Gegenanion ist.
  5. Verfahren gemäß einem der Ansprüche 2 bis 4, weiterhin enthaltend das Trocknen einer Flachdruckplatte, erhalten durch Durchführen des Entwicklungsverfahrens und des Desensibilisierungsverfahrens in dem lichtempfindlichen Flachdruckplattenvorläufer vom Negativtyp nach Belichtung.
  6. Verfahren gemäß einem der Ansprüche 2 bis 4, weiterhin enthaltend: Erwärmen des lichtempfindlichen Flachdruckplattenvorläufers vom Negativtyp nach Belichtung, vor der Durchführung des Entwicklungsverfahrens und des Desensibilisierungsverfahrens und Trocknen einer Flachdruckplatte, erhalten durch Durchführen des Entwicklungsverfahrens und des Desensibilisierungsverfahrens mit dem lichtempfindlichen Flachdruckplattenvorläufer vom Negativtyp nach Entwicklung.
  7. Verfahren gemäß einem der Ansprüche 2 bis 6, worin die Abfallflüssigkeit-Konzentrationsanlage eine Erwärmungsvorrichtung enthält.
  8. Verfahren gemäß Anspruch 7, worin das Erwärmen durchgeführt wird durch Erwärmungsmittel unter Druck, die in der Abfallflüssigkeit-Konzentrationsanlage enthalten sind.
  9. Verfahren gemäß Anspruch 7 oder 8, worin das Erwärmungsmittel, das in der Abfallflüssigkeit-Konzentrationsanlage enthalten ist, eine Wärmepumpe ist, die zumindest eine Wärmefreisetzungseinheit und eine Wärmeabsorptionseinheit enthält und die Plattenerzeugungsverfahren-Abfallflüssigkeit erwärmt wird durch die Wärmefreisetzungseinheit der Wärmepumpe, während der Wasserdampf durch die Wärmeabsorptionseinheit der Wärmepumpe gekühlt wird.
  10. Verfahren gemäß einem der Ansprüche 2 bis 9, worin der Abfallflüssigkeit-Konzentrationsschritt ein Konzentrationssammelschritt zum Sammeln eines Konzentrates der Plattenerzeugungsverfahren-Abfallflüssigkeit, die durch verdampfende Konzentration konzentriert ist, in einen Sammeltank durch Auferlegung von Druck auf das Konzentrat unter Verwendung einer Pumpe enthält.
EP13751553.2A 2012-02-20 2013-01-30 Verfahren zur konzentrierung des flüssigen abfalls aus der druckplattenherstellung, sowie verfahren zur wiederaufbereitung des flüssigen abfalls aus der druckplattenherstellung Not-in-force EP2818930B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012034569 2012-02-20
PCT/JP2013/052106 WO2013125315A1 (ja) 2012-02-20 2013-01-30 製版処理廃液の濃縮方法およびリサイクル方法

Publications (3)

Publication Number Publication Date
EP2818930A1 EP2818930A1 (de) 2014-12-31
EP2818930A4 EP2818930A4 (de) 2015-09-23
EP2818930B1 true EP2818930B1 (de) 2018-08-22

Family

ID=49005506

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13751553.2A Not-in-force EP2818930B1 (de) 2012-02-20 2013-01-30 Verfahren zur konzentrierung des flüssigen abfalls aus der druckplattenherstellung, sowie verfahren zur wiederaufbereitung des flüssigen abfalls aus der druckplattenherstellung

Country Status (5)

Country Link
US (1) US20140345483A1 (de)
EP (1) EP2818930B1 (de)
JP (1) JP5695267B2 (de)
CN (1) CN104115069B (de)
WO (1) WO2013125315A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9943816B2 (en) 2014-10-20 2018-04-17 Eastman Chemical Company Amphoteric ester sulfonates
US9381147B2 (en) 2014-10-20 2016-07-05 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic ester ammonioalkanoates
US9533951B2 (en) 2014-10-20 2017-01-03 Eastman Chemical Company Heterocyclic amphoteric compounds
US11414380B2 (en) * 2015-09-17 2022-08-16 Eastman Chemical Company Amphoteric compounds
US9993408B2 (en) * 2015-09-17 2018-06-12 Johnson & Johnson Consumer Inc. Compositions comprising zwitterionic alkyl-alkanoylamides and/or alkyl alkanoates
KR101759571B1 (ko) * 2017-04-10 2017-07-19 영창케미칼 주식회사 Euv용 감광성 포토레지스트 미세패턴 형성용 현상액 조성물
CN113960897B (zh) * 2021-11-03 2023-09-19 中国科学院光电技术研究所 一种显影装置及方法

Family Cites Families (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4841708B1 (de) 1970-01-13 1973-12-07
DE2064079C2 (de) 1970-12-28 1982-09-09 Hoechst Ag, 6000 Frankfurt Photopolymerisierbares Gemisch
DE2361041C3 (de) 1973-12-07 1980-08-14 Hoechst Ag, 6000 Frankfurt Photopolymerisierbares Gemisch
JPS5311314B2 (de) 1974-09-25 1978-04-20
DE2822190A1 (de) 1978-05-20 1979-11-22 Hoechst Ag Photopolymerisierbares gemisch
DE2822189A1 (de) 1978-05-20 1980-04-17 Hoechst Ag Photopolymerisierbares gemisch
US4252887A (en) 1979-08-14 1981-02-24 E. I. Du Pont De Nemours And Company Dimers derived from unsymmetrical 2,4,5-triphenylimidazole compounds as photoinitiators
DE3036694A1 (de) 1980-09-29 1982-06-03 Hoechst Ag, 6000 Frankfurt Gummielastische, ethylenisch ungesaettigte polyurethane und dieselben enthaltendes durch strahlung polymerisierbares gemisch
DE3048502A1 (de) 1980-12-22 1982-07-22 Hoechst Ag, 6000 Frankfurt Durch strahlung polymerisierbares gemisch und daraus hergestelltes strahlungsempfindliches aufzeichnungsmaterial
JPS5956403A (ja) 1982-09-27 1984-03-31 Mitsubishi Chem Ind Ltd 光重合性組成物
JPH02157084A (ja) 1988-01-12 1990-06-15 Konica Corp 廃液処理の作業性等が改善される非銀塩感光材料の処理方法及び処理装置
JP2587996B2 (ja) * 1988-06-01 1997-03-05 コニカ株式会社 廃液処理の作業性等が改善される非銀塩感光材料の処理方法
JP2655349B2 (ja) 1989-05-18 1997-09-17 富士写真フイルム株式会社 感光性平版印刷版
JP2988756B2 (ja) 1991-04-26 1999-12-13 協和醗酵工業株式会社 光重合開始剤およびこれを含有する光重合性組成物
JP2739395B2 (ja) 1991-08-19 1998-04-15 富士写真フイルム株式会社 感光性平版印刷版
JPH05341535A (ja) 1992-06-09 1993-12-24 Fuji Photo Film Co Ltd 感光性平版印刷版処理装置の廃液回収方法
JP2907643B2 (ja) 1992-07-16 1999-06-21 富士写真フイルム株式会社 感光性平版印刷版およびその処理方法
EP0680626B1 (de) 1993-01-20 1999-06-16 Agfa-Gevaert N.V. Fotopolymerisierbare Zusammensetzung mit hoher Empfindlichkeit und dieseZusammensetzung verwendendes Vefahren zum Herstellen von Bildern
JPH09179297A (ja) 1995-12-22 1997-07-11 Mitsubishi Chem Corp 光重合性組成物
JPH09179296A (ja) 1995-12-22 1997-07-11 Mitsubishi Chem Corp 光重合性組成物
JPH09179298A (ja) 1995-12-22 1997-07-11 Mitsubishi Chem Corp 光重合性組成物
JPH10282679A (ja) 1997-04-08 1998-10-23 Fuji Photo Film Co Ltd ネガ型感光性平版印刷版
JP3839552B2 (ja) 1997-06-03 2006-11-01 コダックポリクロームグラフィックス株式会社 印刷現像感光性平版印刷版及びその製版方法
JP2000250211A (ja) 1999-03-01 2000-09-14 Fuji Photo Film Co Ltd 光重合性組成物
JP2001075279A (ja) 1999-09-03 2001-03-23 Fuji Photo Film Co Ltd 平版印刷版用原版
JP2001133969A (ja) 1999-11-01 2001-05-18 Fuji Photo Film Co Ltd ネガ型平版印刷版原版
JP4092055B2 (ja) 2000-02-09 2008-05-28 三菱製紙株式会社 感光性組成物および感光性平版印刷版材料
JP3449342B2 (ja) 2000-03-30 2003-09-22 三菱化学株式会社 光硬化性組成物、低複屈折光学部材及びその製造方法
JP2002023360A (ja) 2000-07-12 2002-01-23 Fuji Photo Film Co Ltd ネガ型画像記録材料
JP4156784B2 (ja) 2000-07-25 2008-09-24 富士フイルム株式会社 ネガ型画像記録材料及び画像形成方法
JP4319363B2 (ja) 2001-01-15 2009-08-26 富士フイルム株式会社 ネガ型画像記録材料
JP4414607B2 (ja) 2001-03-14 2010-02-10 富士フイルム株式会社 ラジカル重合性化合物
JP2002287344A (ja) 2001-03-27 2002-10-03 Fuji Photo Film Co Ltd 光重合性平版印刷版
US20030118939A1 (en) 2001-11-09 2003-06-26 Kodak Polychrome Graphics, L.L.C. High speed negative working thermal printing plates
US7208263B2 (en) * 2001-07-06 2007-04-24 Toray Industries, Inc. Method for manufacturing photosensitive resin printing plate, and developer treatment device
JP2003064130A (ja) 2001-08-29 2003-03-05 Fuji Photo Film Co Ltd 光重合性組成物
JP2003270781A (ja) * 2002-03-18 2003-09-25 Fuji Photo Film Co Ltd 画像記録材料
JP3989270B2 (ja) 2002-03-25 2007-10-10 富士フイルム株式会社 光重合性組成物
EP1359008B1 (de) 2002-04-29 2005-08-31 Agfa-Gevaert Strahlungsempfindliches Gemisch, damit hergestelltes Aufzeichnungsmaterial, und Verfahren zur Herstellung einer Druckplatte
JP2004070031A (ja) * 2002-08-07 2004-03-04 Asahi Kasei Chemicals Corp 感光性樹脂版現像液の処理方法
JP4466821B2 (ja) 2002-09-30 2010-05-26 富士フイルム株式会社 重合性組成物及び平版印刷版原版
DE10255663B4 (de) 2002-11-28 2006-05-04 Kodak Polychrome Graphics Gmbh Strahlungsempfindliche Elemente
JP4458778B2 (ja) 2003-02-20 2010-04-28 富士フイルム株式会社 重合性組成物及びそれを用いた平版印刷版原版
JP4299032B2 (ja) 2003-03-28 2009-07-22 三菱製紙株式会社 感光性平版印刷版材料
JP2005010264A (ja) * 2003-06-17 2005-01-13 Konica Minolta Medical & Graphic Inc 感光性平版印刷版の処理方法及び現像液の劣化低減方法
ATE491968T1 (de) 2003-07-22 2011-01-15 Fujifilm Corp Flachdruckplattenvorläufer und lithographisches druckverfahren
DE04766666T1 (de) 2003-09-22 2009-02-05 Agfa Graphics N.V. Fotopolymer-druckplatten-vorläufer
JP4815113B2 (ja) 2003-09-24 2011-11-16 富士フイルム株式会社 平版印刷版原版および平版印刷方法
JP4644458B2 (ja) 2003-09-30 2011-03-02 富士フイルム株式会社 平版印刷版原版および平版印刷方法
JP4401262B2 (ja) 2004-02-02 2010-01-20 富士フイルム株式会社 平版印刷版原版
JP4319567B2 (ja) 2004-03-04 2009-08-26 富士フイルム株式会社 重合性組成物及び平版印刷版原版
JP4351933B2 (ja) 2004-03-05 2009-10-28 富士フイルム株式会社 ネガ型平版印刷版原版およびこれを用いた平版印刷版の製版方法
JP2006065210A (ja) 2004-08-30 2006-03-09 Fuji Photo Film Co Ltd 感光性平版印刷版
JP2006189604A (ja) 2005-01-06 2006-07-20 Konica Minolta Medical & Graphic Inc 光重合性組成物、感光性平版印刷版材料および平版印刷版の製造方法
JP4469734B2 (ja) 2005-02-03 2010-05-26 富士フイルム株式会社 平版印刷版原版
JP2006239867A (ja) 2005-02-28 2006-09-14 Fuji Photo Film Co Ltd 平版印刷版原版および平版印刷方法
JP2006243493A (ja) 2005-03-04 2006-09-14 Fuji Photo Film Co Ltd 感光性平版印刷版
JP4393408B2 (ja) 2005-03-16 2010-01-06 富士フイルム株式会社 ネガ型平版印刷版原版
JP2006309160A (ja) * 2005-03-29 2006-11-09 Fuji Photo Film Co Ltd 平版印刷版の製版方法
JP4792326B2 (ja) 2005-07-25 2011-10-12 富士フイルム株式会社 平版印刷版の作製方法および平版印刷版原版
US7153632B1 (en) 2005-08-03 2006-12-26 Eastman Kodak Company Radiation-sensitive compositions and imageable materials
JP5170960B2 (ja) 2005-08-29 2013-03-27 富士フイルム株式会社 平版印刷版原版、及び平版印刷方法
JP4666488B2 (ja) 2005-09-07 2011-04-06 株式会社竹中工務店 物品のレイアウト支援システム
JP2007093866A (ja) 2005-09-28 2007-04-12 Fujifilm Corp 感光性組成物および平版印刷版原版
JP2007094138A (ja) 2005-09-29 2007-04-12 Fujifilm Corp 平版印刷版原版及びその製版方法
JP4911457B2 (ja) 2005-12-02 2012-04-04 富士フイルム株式会社 平版印刷版の作製方法および平版印刷版原版
JP4820640B2 (ja) 2005-12-20 2011-11-24 富士フイルム株式会社 平版印刷版の作製方法
JP4719574B2 (ja) 2006-01-12 2011-07-06 富士フイルム株式会社 平版印刷版原版
JP2007206216A (ja) 2006-01-31 2007-08-16 Fujifilm Corp 平版印刷版の作製方法および平版印刷版原版
JP2007206217A (ja) 2006-01-31 2007-08-16 Fujifilm Corp 平版印刷版の作製方法および平版印刷版原版
JP2007225702A (ja) 2006-02-21 2007-09-06 Fujifilm Corp 平版印刷版の作製方法
JP2007225701A (ja) 2006-02-21 2007-09-06 Fujifilm Corp 平版印刷版の作製方法
ATE517758T1 (de) * 2006-03-17 2011-08-15 Agfa Graphics Nv Verfahren zur herstellung einer lithografiedruckform
JP2007293221A (ja) 2006-03-31 2007-11-08 Fujifilm Corp 平版印刷版の作製方法及び平版印刷版原版
JP4796890B2 (ja) 2006-03-31 2011-10-19 富士フイルム株式会社 平版印刷版原版及び平版印刷方法
JP2007328243A (ja) 2006-06-09 2007-12-20 Fujifilm Corp 平版印刷版の作製方法および平版印刷版原版
JP2008080229A (ja) * 2006-09-27 2008-04-10 Toyobo Co Ltd 水現像性感光性樹脂現像廃液の処理方法
JP2008195018A (ja) 2007-02-15 2008-08-28 Fujifilm Corp 平版印刷版原版および平版印刷方法
JP2008233660A (ja) 2007-03-22 2008-10-02 Fujifilm Corp 浸漬型平版印刷版用自動現像装置およびその方法
JP4991430B2 (ja) 2007-03-30 2012-08-01 富士フイルム株式会社 平版印刷版原版
JP4826918B2 (ja) 2007-04-03 2011-11-30 三菱化学株式会社 光重合性組成物
JP5364513B2 (ja) * 2008-09-12 2013-12-11 富士フイルム株式会社 平版印刷版原版用現像液及び平版印刷版の製造方法
JP4774124B1 (ja) * 2009-09-24 2011-09-14 富士フイルムグラフィックシステムズ株式会社 平版印刷版現像廃液削減装置
JP2011090282A (ja) 2009-09-25 2011-05-06 Fujifilm Corp 感光性平版印刷版の製版処理廃液の処理方法
JP5751483B2 (ja) 2010-06-28 2015-07-22 東芝ライテック株式会社 スイッチング電源用装置、スイッチング電源回路および電気機器
JP5714544B2 (ja) * 2011-09-15 2015-05-07 富士フイルム株式会社 製版処理廃液のリサイクル方法
EP2762977B1 (de) * 2011-11-04 2017-09-27 FUJIFILM Corporation Verfahren zur wiederverwertung von ablaugen aus der plattenherstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JPWO2013125315A1 (ja) 2015-07-30
CN104115069B (zh) 2018-11-02
JP5695267B2 (ja) 2015-04-01
EP2818930A4 (de) 2015-09-23
EP2818930A1 (de) 2014-12-31
WO2013125315A1 (ja) 2013-08-29
CN104115069A (zh) 2014-10-22
US20140345483A1 (en) 2014-11-27

Similar Documents

Publication Publication Date Title
EP2818930B1 (de) Verfahren zur konzentrierung des flüssigen abfalls aus der druckplattenherstellung, sowie verfahren zur wiederaufbereitung des flüssigen abfalls aus der druckplattenherstellung
EP3543790A1 (de) Strahlungsempfindliche zusammensetzung, originalplatte für lithografische druckplatte und verfahren zur herstellung einer lithografischen druckplatte
EP2541326B1 (de) Verfahren zur herstellung einer planographie-druckplatte und entwicklerlösung für eine master-planographie-druckplatte
EP2610673B1 (de) Verfahren zur Herstellung von Lithografiedruckplatten
EP2975461B1 (de) Konzentrationsverfahren für fluidabfälle aus einer druckformherstellung und recyclingverfahren
CN110891797B (zh) 平版印刷版的制作方法
JP6081458B2 (ja) 現像処理廃液濃縮方法及び現像処理廃液のリサイクル方法
EP2757417B1 (de) Verfahren zur wiederverwertung von abwasser durch ein plattenherstellungsverfahren
EP3831613B1 (de) Flachdruckplattenvorläufer
EP3858629A1 (de) Originalplatte zum drucken, laminat aus originalplatte zum drucken, verfahren zur herstellung einer druckplatte und druckverfahren
EP2204698B1 (de) Plattenoberflächenbehandlungsmittel für eine lithografische Druckplatte und Verfahren zur Behandlung der lithografischen Druckplatte
EP3564755B1 (de) Verfahren zur herstellung einer flachdruckplatte
EP3858636A1 (de) Originalplatte zum drucken, laminat aus originalplatte zum drucken, verfahren zur druckplattenherstellung und druckverfahren
EP2103993B1 (de) Automatische Verarbeitung zur Herstellung einer Lithografiedruckplatte
EP2762977B1 (de) Verfahren zur wiederverwertung von ablaugen aus der plattenherstellung
JP5448670B2 (ja) 平版印刷版用版面処理剤、及び、平版印刷版の処理方法
WO2020174843A1 (ja) 平版印刷版の製版方法
JP4813432B2 (ja) 平版印刷版の製版方法
JP2006350076A (ja) 自動現像処理装置および平版印刷版
JPS63194266A (ja) 現像処理の安定性等が改良される感光性平版印刷版の処理方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140819

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: IMAIZUMI, MITSUHIRO

Inventor name: WATANABE, TOSHIHIRO

RA4 Supplementary search report drawn up and despatched (corrected)

Effective date: 20150821

RIC1 Information provided on ipc code assigned before grant

Ipc: C02F 1/04 20060101ALI20150817BHEP

Ipc: G03F 7/00 20060101ALI20150817BHEP

Ipc: G03F 7/32 20060101AFI20150817BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170905

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602013042410

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: G03F0007320000

Ipc: G03F0007300000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: G03F 7/027 20060101ALI20180302BHEP

Ipc: G03F 7/30 20060101AFI20180302BHEP

Ipc: G03F 7/32 20060101ALI20180302BHEP

INTG Intention to grant announced

Effective date: 20180328

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1033171

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013042410

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180822

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181123

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181122

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181222

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181122

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1033171

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013042410

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190130

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190131

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20200114

Year of fee payment: 8

Ref country code: GB

Payment date: 20200122

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181222

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130130

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602013042410

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210803

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180822